NASA/TP-2014-217393

Organic Contamination Baseline Study in NASA Johnson Space Center Astromaterials Curation Laboratories

NASA Astromaterials Acquisition and Curation Office

Michael J. Calaway

JACOBS

Johnson Space Center, Houston, Texas

Carlton C. Allen, Ph.D.

NASA

Johnson Space Center, Houston, Texas

Judith H. Allton

NASA

Johnson Space Center, Houston, Texas

July 2014

https://ntrs.nasa.gov/search.jsp?R=20150015645 2020-07-19T03:38:33+00:00Z

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NASA/TP-2014-217393

Organic Contamination Baseline Study in NASA Johnson Space Center Astromaterials Curation Laboratories

NASA Astromaterials Acquisition and Curation Office

Michael J. Calaway

JACOBS

Johnson Space Center, Houston, Texas

Carlton C. Allen, Ph.D.

NASA

Johnson Space Center, Houston, Texas

Judith H. Allton

NASA

Johnson Space Center, Houston, Texas

July 2014

Acknowledgments

We would first like to thank all Johnson Space Center (JSC) Astromaterial Research and Exploration

Science (ARES) Directorate employees, civil servants, and contractors for their direct and indirect help on

this effort. In addition, Air-Liquide-Balazs Analytical Services was contracted to conduct the TD-GC-

MS, GC-MS, and NVR/FT-IR analyses for this fiscal year 2012 study. Specifically, Dr. Hugh Gotts,

Steve Popst, and Reggie Davison of Air-Liquide-Balazs Analytical Services provided exceptional

analytical services and contributed to the experimental design and procedures for measuring organics in

the curation gloveboxes. Linda Watts and Dr. Ryan Zeigler are thanked for their help during sampling of

the organics in the Lunar Curation Laboratory. Melissa Rodriguez and Joshua McConnell are thanked for

their help during sampling of the organics in the Advanced Curation Laboratory. Dr. Patti Jo Burkett is

thanked for running ultrapure water particle counts in the Genesis Laboratory. We would also like to

acknowledge the work completed by our highly trained curation technician team. Robert McCandless,

Donna Lisa Owens, Rosa Ayala, and Anthony Farrell completed the NASA JSC technical support

procedure 23 for both gloveboxes. Steven Sendejo and Joe Falcon, along with the JSC riggers, completed

the advanced curation glovebox relocation for cleaning and refitting the glovebox nitrogen supply lines.

Finally, we would like to thank Dr. Marc Fries as the assigned NASA technical publication manuscript

reviewer who supplied critical comments.

Available from:

NASA Center for AeroSpace Information National Technical Information Service

7121 Standard Drive 5285 Port Royal Road

Hanover, MD 21076-1320 Springfield, VA 22161

This report is also available in electronic form at http://ston.jsc.nasa.gov/collections/TRS

i

Preface

The organic contamination baseline study has been the largest effort in understanding the role of organics

in Johnson Space Center (JSC) astromaterials curation laboratories in the over 40-year history of these

facilities. Scientific study of organic contamination on spacecraft and facilities will become increasingly

important as NASA continues to explore the solar system well into the 21st century. The Apollo manned

lunar landing program was the last NASA program that focused an enormous effort toward understanding

organic contamination and mitigation. As we studied the historical data on organics from the Lunar

Receiving Laboratory, it became apparent that the amount of work, volume of laboratory analyses, and

scientific dedication applied by the Apollo team in such a short period of time were truly awe inspiring.

Organic studies since Apollo have been limited by comparison, although they have all made significant

contributions of their own to furthering the knowledge and understanding of contamination on NASA

spacecraft and facilities.

In recent years, we have mainly focused our research on organic contamination by carbonaceous

compounds of seven carbon atoms and greater (> C7). However, much more work is required to progress

our understanding of organic contamination in JSC astromaterials curation laboratories. In the coming

years, we hope to extend the organic baseline study to include organics of C1 to C6. In addition, the role

of polycyclic aromatic hydrocarbons, bacteria, and amino acids will be paramount for future exploration

missions that feature an astrobiology component. This new line of research will be an important effort in

JSC curation and will comprise a continuing effort.

For this NASA technical publication, we wanted to document the state of our current knowledge on

organic contamination and disseminate what we know so far in order to help our colleagues planning

upcoming missions for NASA. Furthermore, we hoped that this study will promote improvements to JSC

curation laboratory procedures and to routine monitoring of today’s astromaterial collections. We set out

to compile all unpublished, historical, curation-related documents at JSC and study them in a holistic

manner. In addition, we sought to conduct research where we found knowledge gaps from past studies. I

hope the information found in this publication accomplished these goals and will be a resource for future

scientists. We anticipate the organic contamination baseline study will be just one step toward designing

better missions, improving the curation of today’s astromaterial collections, and inspiring more scientists

to focus on understanding terrestrial contamination and cross-contamination of pristine astromaterials.

These efforts will secure the scientific integrity of each new sample.

Michael J. Calaway

Advanced Exploration Science and Curation Project Lead

JACOBS at NASA Johnson Space Center

April 21, 2014

Houston, TX

ii

Table of Contents Preface ...................................................................................................................................................... i

List of Figures ........................................................................................................................................... iv

List of Acronyms ...................................................................................................................................... vi

1.0 INTRODUCTION ............................................................................................................................. 1

2.0 HISTORICAL ORGANIC CONTAMINATION RECORDS .......................................................... 4

2.1 Apollo Program and the Lunar Receiving Laboratory ................................................................ 4

2.1.1 Lunar Receiving Laboratory Simulations and Cold Trap Analyses .................................. 7

2.1.2 Lunar Receiving Laboratory Ottawa Sand Organic Monitors ........................................... 9

2.1.3 Lunar Receiving Laboratory and White Sands Test Facility Tool Cleaning ..................... 12

2.1.4 Lunar Receiving Laboratory Organic Results Summary ................................................... 14

2.1.5 Lunar Receiving Laboratory Biological Containment ....................................................... 16

2.2 Establishing the Lunar Curation Laboratory 1973 to 1979 ......................................................... 18

2.3 Xylan Contamination and Lessons Learned 1972 to 1990 .......................................................... 18

2.4 Organic Contamination Review Group 1997 .............................................................................. 21

2.5 Glovebox Organic Contamination Results 1998 to Present ........................................................ 23

2.5.1 1998 Meteorite Laboratory Organic Analyses ................................................................... 23

2.5.2 Dixon Report: Evaluation of Organic Contamination in Curation .................................... 25

2.5.3 White Sands Test Facility Glovebox Glove Analyses ....................................................... 30

2.5.4 Contamination by Glovebox Materials: A Case Study ...................................................... 31

2.6 Cleanroom Organic Contamination Results 2000 to Present ...................................................... 34

2.6.1 Genesis Laboratory Organic Analyses ............................................................................... 35

2.6.2 Camenzind Report: Evaluation of Cleanroom Contamination .......................................... 42

2.6.3 Outside Air Organic Analysis ............................................................................................ 43

iii

3.0 ORGANIC CONTAMINATION BASELINE 2012 ......................................................................... 44

3.1 Standard Glovebox Cleaning ....................................................................................................... 47

3.2 Liquid Particle Counts from Glovebox Cleaning ........................................................................ 48

3.3 Scanning Electron Microscope Particle Identification from Glovebox Cleaning ....................... 49

3.4 Vertical and Surface Wafer Exposure Thermal Desorption Gas Chromatography Mass

Spectroscopy Analysis ............................................................................................................... 56

3.5 Air Absorbent Thermal Desorption Gas Chromatography Mass Spectroscopy Analysis ........... 63

3.6 Surface Methylene Chloride Exposure Non Volatile Residue/Fourier Transform Infrared

Spectroscopy and Gas Chromatography Mass Spectroscopy Analysis ..................................... 67

4.0 SUMMARY ....................................................................................................................................... 70

5.0 APPENDIX I – Identified Organic Compounds in Johnson Space Center Curation Laboratories ... 76

6.0 APPENDIX II – Johnson Space Center 03243 Glovebox Cleaning Procedure: 1981 ...................... 80

7.0 APPENDIX III – Technical Support Procedure 23 – Glovebox Cleaning: version March 8, 2011 .. 85

8.0 REFERENCES .................................................................................................................................. 88

iv

List of Figures

Figure 1: High Vacuum Complex during construction of the Lunar Receiving Laboratory in 1968

(NASA Photo # S68-25212) ......................................................................................................... 5

Figure 2: Components of the High Vacuum Complex in the Lunar Receiving Laboratory (White

1976:3) .......................................................................................................................................... 5

Figure 3: R-cabinets (Atmospheric Decontamination Cabinets) during construction of the High

Vacuum Complex in 1968 (NASA Photo # S68-25204).............................................................. 6

Figure 4: LRL Apollo 11 Ottawa sand organic monitoring results (Simoneit and Flory 1971) ................ 10

Figure 5: LRL Apollo 12 Ottawa sand organic monitoring results (Simoneit and Flory 1971) ................ 11

Figure 6: Compilation of known LRL organic contaminates (Flory and Simoneit 1972; Simoneit et al.

1973; Simoneit and Flory 1971) ................................................................................................. 15

Figure 7: SNAP Line in LRL during Apollo 14 in 1971 (NASA Photo # S-71-19264) ............................ 17

Figure 8: 1998 Balazs Report .................................................................................................................... 24

Figure 9: Lunar Lab Glovebox Apollo 16 – Cabinet 307-38 (PSL-38) ..................................................... 26

Figure 10: Lunar Lab Glovebox – Cabinet 309-49 (RSL-49) .................................................................... 26

Figure 11: Mars Meteorite cabinet in the Meteorite Curation Laboratory ................................................. 26

Figure 12: January 2000 Balazs Report ..................................................................................................... 27

Figure 13: April 2000 Balazs Report ......................................................................................................... 29

Figure 14: 2001 WSTF outgassing test results from glovebox gloves ...................................................... 30

Figure 15: 2008 MBraun glovebox in B31N, Room 1106......................................................................... 32

Figure 16: 2008 Balazs organic wafer testing on cold plate and weighing balance .................................. 32

Figure 17: 2008 Balazs results for the MBraun glovebox organic testing ................................................. 32

Figure 18: 2012 Balazs report for the MBraun glovebox organic testing for the Hayabusa

Laboratory .................................................................................................................................. 33

Figure 19: Balazs wafer exposure TD-GC-MS results for Genesis Laboratory from 2000 to 2001 ......... 36

Figure 20: Balazs adsorbent tube TD-GC-MS results for Genesis Laboratory from 2001 and 2002 ........ 37

Figure 21: Balazs wafer exposure TD-GC-MS results for Genesis Laboratory from 2002 to 2004 ......... 38

Figure 22: Balazs wafer exposure TD-GC-MS results for Genesis Laboratory from 2005 to 2011 ......... 39

Figure 23: Genesis Laboratory measured > C7 hydrocarbons from 2000 to 2011 ..................................... 41

Figure 24: 2004 Balazs adsorbent tube TD-GC-MS results for GN2 in the Genesis Laboratory .............. 41

Figure 25: JSC toxicology results in 2000 for Genesis Lab, Meteorite Lab, and JSC outside air ............. 43

Figure 26: ISO class 5 cleanroom with ACG ............................................................................................ 45

Figure 27: ACG inside the ISO class 5 cleanroom .................................................................................... 45

Figure 28: ACG after TSP 23 cleaning ...................................................................................................... 45

Figure 29: PSL inside the Lunar laboratory, B31N ................................................................................... 45

Figure 30: LCG located in the PSL inside an ISO Class 6 cleanroom environment ................................. 45

Figure 31: MIL-STD 1246C cleanliness Level 50 ..................................................................................... 47

Figure 32: LCG UPW cleaning ................................................................................................................. 47

Figure 33: Stereomicroscope particle inspection of filter paper from UPW rinse ..................................... 47

Figure 34: ACG UPW particle counts from TSP 23 cleaning ................................................................... 49

v

Figure 35: LCG UPW particle counts from TSP 23 cleaning .................................................................... 49

Figure 36: LCG SEM particle identification on 20 micron pore size filter ............................................... 50

Figure 37: Chart for LCG SEM particle identification on 20 micron pore size filter ................................ 51

Figure 38: LCG SEM particle identification on 0.8 micron pore size filter .............................................. 51

Figure 39: Chart for LCG SEM particle identification on 0.8 micron pore size filter ............................... 52

Figure 40: ACG SEM particle identification on 0.8 micron pore size filter .............................................. 52

Figure 41: Chart for ACG SEM particle identification on 0.8 micron pore size filter .............................. 53

Figure 42: SEM image and chemistry of unknown organic particle with a carbon signature ................... 53

Figure 43: SEM image and chemistry of unknown organic fiber with carbon and oxygen signature ....... 54

Figure 44: SEM image and chemistry of unknown organic particle with carbon and oxygen signature .. 54

Figure 45: SEM image and chemistry of unknown organic particle with carbon and oxygen signature .. 54

Figure 46: SEM image and chemistry of unknown organic particle/fiber with carbon, nitrogen, and

oxygen signature ......................................................................................................................... 55

Figure 47: SEM image and chemistry of unknown organic particle with silicone, oxygen, and carbon

signature; possibly silicone ......................................................................................................... 55

Figure 48: General chart for LCG SEM particle identification ................................................................. 56

Figure 49: General chart for ACG SEM particle identification ................................................................. 56

Figure 50: Lunar material being processed inside LCG during testing ..................................................... 57

Figure 51: 8” silicon wafers exposed during organic testing inside the LCG ............................................ 57

Figure 52: 6” silicon wafer surface exposure ............................................................................................. 57

Figure 53: 6” silicon wafer vertical exposure in the ACG ......................................................................... 57

Figure 54: Silicon wafer handling during the ACG organic testing .......................................................... 57

Figure 55: LCG Balazs organic wafer test results ..................................................................................... 59

Figure 56: LCG Balazs organic wafer TD-GC-MS plot for vertical wafer exposure ................................ 59

Figure 57: LCG Balazs organic wafer TD-GC-MS plot for surface wafer exposure ................................ 60

Figure 58: ACG Balazs organic wafer test results ..................................................................................... 61

Figure 59: ACG Balazs organic wafer TD-GC-MS plot for vertical wafer exposure ............................... 62

Figure 60: ACG Balazs organic wafer TD-GC-MS plot for surface wafer exposure ................................ 62

Figure 61: Location of adsorbent tube attachment to main chamber of the ACG ..................................... 63

Figure 62: Location of adsorbent tube attachment to main chamber of the LCG ...................................... 63

Figure 63: Gilian sampling pump and adsorbent tube for collecting organics in air ................................. 64

Figure 64: LCG Balazs results for adsorbent tube ..................................................................................... 65

Figure 65: ACG Balazs results for adsorbent tube..................................................................................... 65

Figure 66: Balazs TD-GC-MS results for GN2 supply organic testing in 2013 ........................................ 66

Figure 67: ISO-AMC air cleanliness class; ISO 14644-8 .......................................................................... 66

Figure 68: Application of methylene chloride to the surface of the ACG with glass syringe ................... 67

Figure 69: Collection of methylene chloride to the surface of the ACG with glass syringe...................... 67

Figure 70: ACG Balazs plot for NVR/FT-IR results ................................................................................. 68

Figure 71: ACG Balazs plot for GC-MS results ........................................................................................ 69

vi

List of Acronyms

ACG Advanced Curation Glovebox

ALHT Apollo Lunar Hand Tools

ALSRC Apollo Lunar Sample Return Container

AMC Airborne Molecular Contamination

ANSMET Antarctic Search for Meteorites

ARC Ames Research Center

ARES Astromaterial Research and Exploration Science (a NASA JSC Directorate)

B31 Building 31 (at NASA JSC)

B31N Building 31 North (at NASA JSC)

BHT Butylated Hydroxy Toluene

CAPTEM Curation and Analysis Planning Team for Extraterrestrial Materials

CCO Contamination Control Officer

CDC Center for Disease Control

CP Chemically Pure

CSM Chlorosulfonated polyethylene

DBF Dibutylformamide

DBP Dibutyl phthalate

DEHP Di-2-ethylhexyl phthalate

DEP Diethyl phthalate

DI Deionized

DIBP Diisobutyl phthalate

DMF N, N – Dimethylformamide

DNA Deoxyribonucleic Acid

DNP Dinonyl phthalate

DOP Dioctyl phthalate

FEP Fluorinated Ethylene Propylene

FE-SEM Field Emission Scanning Electron Microscope

FFU Fan Filter Unit

FT-IR Fourier Transform Infrared Spectroscopy

FY Fiscal Year

GAL Gas Analysis Laboratory

GC Gas Chromatography

GC-MS Gas Chromatography Mass Spectroscopy

GLC-MS Gas Liquid Chromatography – Mass Spectrometry

GN2 Gaseous Nitrogen

HEPA High-Efficiency Particulate Air

ICBC Interagency Committee on Back Contamination

IPA Isopropyl alcohol

IR&D Innovative Research and Development

ISO International Organization for Standardization

JAXA Japan Aerospace Exploration Agency

vii

JSC Johnson Space Center

LABe Low Angled Backscatter Electron

LAPST Lunar and Planetary Science Team

LCG Lunar Curation Glovebox

LM Lunar Module

LN2 Liquid Nitrogen

LRL Lunar Receiving Laboratory

LSAPT Lunar Sample Analysis Planning Team

LSPET Lunar Sample Preliminary Examination Team

MCE Mixed Cellulose Ester

MEKP Methyl ethyl ketone peroxide

MET Meteorite Hills (Antarctica Meteorite Recovery location)

MIBK Methyl Isobutyl Ketone

MIL-STD Military Standard

MPL Meteorite Processing Laboratory (in Meteorite Laboratory in JSC B31)

MRSH Mars Return Sample and Handling

MSC Manned Spacecraft Center (currently JSC)

MSD Mass Selective Detector

NASA National Aeronautics and Space Administration

NBBS +N-Butylbenzenesulphonamide

NMP N-Methyl-2-Pyrrolidone

NNPL Nonsterile Nitrogen Processing Line

NSCORT NASA Specialized Center of Research and Training

NVR Non Volatile Residue

NVR/FT-IR Non Volatile Residue/ Fourier Transform Infrared Spectroscopy

OCT Office of the Chief Technologist

OGA Organic Gas Analysis

OM Organic Monitor

PAH Polycyclic Aromatic Hydrocarbon

PCA Precision Cleaning Agent

PET Preliminary Examination Team

PFA Perfluoroalkoxy

PGMEA Propylene glycol monomethyl ether acetate

PI Principal Investigator

PLSS Primary Life Support System

PSL Pristine Sample Laboratory (in Lunar Laboratory JSC B31N)

PTFE Polytetrafluoroethene

PU Polyurethane

PVC Poly Vinyl Chloride

RCL Radiation Counting Lab

RNA Ribonucleic Acid

RO Reverse Osmosis

RSL Return Sample Laboratory (in Lunar Laboratory JSC B31N)

SCFH Standard Cubic Feet per Hour

viii

SEM Scanning Electron Microscope

SESC Special Environmental Sample Container

SIM Simulation

SNAP Sterile Nitrogen Atmospheric Processing

SS Stainless Steel

TBP Tri-n-butyl phosphate

TCE Trichloroethylene

TCEP Tris(2-carboxyethyl)phosphine

TD-GC-MS Thermal Desorption Gas Chromatography Mass Spectroscopy

TFE Tetrafluoroethylene

THC Total Hydrocarbon Count

TIC Total Ion Count

TOC Total Organic Carbon

TSP Technical Support Procedure

TVOC Total Volatile Organic Compounds

TXIB 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate

UCB-SSL University of California Berkley – Space Science Laboratory

UCLA University of California – Los Angeles

ULPA Ultra-Low Penetration Air

UPW Ultra-pure Water

VOC Volatile Organic Compound

WSTF White Sands Test Facility

XPS X-ray Photoelectron Spectroscopy

1

1.0 INTRODUCTION

Future robotic and human spaceflight missions to the Moon, Mars, asteroids, and comets will require

curating astromaterial samples with minimal inorganic and organic contamination to preserve the

scientific integrity of each sample. The importance of proper curation has been recognized since NASA’s

first sample return efforts. During the Apollo program, terrestrial organic contamination was initially a

great concern along with terrestrial inorganic contamination to lunar samples. Since the Apollo program

ended, however, the lunar sample collection has been primarily concerned with inorganic contamination.

Genesis and Stardust sample return missions have also been primarily concerned with particulate

inorganic contamination, although organic reference materials and witness plates were archived.

However, future missions will focus on strict protocols for reducing organic contamination that have not

been seen in over 40 years. For example, OSIRIS-REx and Hayabusa-2 are two currently planned robotic

sample return missions to carbon-rich asteroids. These missions will impose stringent new requirements

for a reduction and characterization of organic contamination when compared to previous sample return

mission practices. In addition, a future Mars Sample Return mission will have even more rigid protocols

and procedural requirements on organic cleanliness as well as biological pathogen containment.

To properly curate these materials, the Astromaterials Acquisition and Curation Office under the

Astromaterial Research and Exploration Science (ARES) Directorate at NASA Johnson Space Center

(JSC) houses and protects all extraterrestrial materials brought back to Earth that are controlled by the

United States government. As of 2014, the NASA Astromaterials Acquisition and Curation Office is

responsible for the following sample collections:

Apollo program lunar rocks and soils (est. 1969) and a subset of Soviet Union Luna program

lunar material (est. 1971) – curated in an International Organization for Standardization (ISO)

Class 6 cleanroom with glovebox isolation technology

Meteorites – Antarctic Search for Meteorites (ANSMET) program (est. 1977) – ISO Class 6

cleanroom with glovebox isolation technology

Cosmic Dust collected from high altitude aircraft (est. 1981) – ISO Class 5 cleanroom

Space Exposed Hardware (est. 1985) – ISO Class 7 cleanroom

Genesis Solar Wind Mission (est. 2004) – ISO Class 4 cleanroom

Stardust Comet / Interstellar Dust Mission (est. 2006) – ISO Class 5 cleanroom

Subset of Hayabusa Japan Aerospace Exploration Agency (JAXA) Asteroid Mission (est.

2012) – ISO Class 5 cleanroom with glovebox isolation technology

(Note: ISO 14644-1 Cleanroom Class determined by 2007 to 2012 weekly particle counts)

For over 40 years, the Astromaterials Acquisition and Curation Office has generated a legacy of

preserving extraterrestrial samples in clean isolation and distributing these samples to the international

scientific community. These samples are utilized for analytical investigations and for public displays

throughout the world. Today, JSC curation stores and processes samples in seven major laboratory

cleanrooms ranging from ISO class 7 to ISO class 4. Depending on the sample collection, samples are

handled and stored in over 43 gaseous nitrogen gloveboxes, numerous gaseous nitrogen desiccators for

long-term storage, class 100 flow benches, and/or cleanrooms. All curation laboratories have strict

protocols for daily cleaning, daily monitoring, and material requirements for use in the laboratories to

reduce cross-contamination with the samples. Materials entering the curation labs must have both low

2

outgassing and low particle shedding properties. In addition, sample containers, handling tools, and

enclosures are routinely cleaned using well-established laboratory protocols and procedures. The result is

a series of world-class scientific collections that forms an important foundation for the continuing

progress of the planetary science, astrobiology, and related scientific communities.

After the Apollo program ended in 1972, the Apollo curation laboratories required little monitoring of

organic contamination. This is because most laboratories that studied Apollo material were primarily

concerned with inorganic contamination to their sample collections. However, organic studies have been

conducted periodically in Lunar, Meteorite, and Genesis curation laboratories as directed by the Curation

and Analysis Planning Team for Extraterrestrial Materials (CAPTEM), a NASA oversight committee, by

the NASA JSC Contamination Control Officer (CCO), or by curators and/or individual principal

investigators (PIs) upon request. The first effort to understand organic contamination was during the

Apollo program. JSC’s Lunar Receiving Laboratory (LRL), which was tasked with initial receipt of

Apollo samples, conducted comprehensive studies on organics before and after Apollo 11 returned with

samples in 1969. In addition, the program conducted many biological investigations on lunar returned

materials. After the Apollo program, the next notable organic study (1986-1990) stemmed from the

investigation of a lubricant compound named Xylan that was widely used in curation laboratories and was

found to create a contamination risk. The largest Meteorite laboratory organic analysis was initiated in

1996 after publication of hypothesized biosignatures in the Martian meteorite ALH84001 and the

subsequent findings of the Organic Contamination Working Group in 1997. This prompted additional

organic testing in the Meteorite lab and reexamination of curation procedures overall, to include debate on

issues such as the use of nylon bags for sample storage. Between 1998 and 2001, other organic

contamination studies were developed alongside discussion of prospects for a Mars sample return

mission. Genesis, the first samples returned since Apollo, was primarily concerned with organic

contamination that could easily adhere to the highly pure semiconductor collectors during assembly of the

spacecraft payload. Since the construction of the ISO class 4 laminar flow Genesis curation laboratory in

1999, airborne molecular contamination data have been measured in a systematic manner. Thus, airborne

molecular contamination was documented during payload assembly in a newly built cleanroom,

documented as the cleanroom aged and when facility changes were made, and continues today. While

individual organic investigations have been carried out sporadically for over 40 years, no organic study or

committee to date has taken a look at all JSC curation laboratories in a holistic study since the days of the

Apollo program. The Organic Contamination Baseline Study in JSC Curation Laboratories was

established to give CAPTEM, future mission planning teams, and PIs who work with astromaterial

samples an understating of the current state of organic contamination in NASA JSC curation laboratories.

This study was supported by the NASA Innovative Research and Development (IR&D) initiative through

the Office of the Chief Technologist (OCT) at JSC, to plan for future missions that require clean handling

and storage of samples with an emphasis on analyzing samples for both inorganic and organic

contaminates.

During fiscal year (FY) 2012, we conducted a year-long project to compile historical documentation and

laboratory tests involving organic investigations. In addition, we developed a plan to determine the

current state of organic cleanliness in curation laboratories housing astromaterials. This was

accomplished by focusing on current procedures and protocols for cleaning, sample handling, and storage.

It should be noted that we have attempted to incorporate all relevant historical testing data for gloveboxes

and cleanrooms that are found in JSC records. We augmented these studies with examination of

glovebox sample processing to narrow the gap in our understanding of cleanliness during glovebox

3

processing. While the Genesis laboratory has performed numerous organic analyses of their ISO class 4

cleanroom environment, historically few analyses have been conducted inside gloveboxes themselves.

This is important because future sample return missions concerned with organics will most likely use a

form of glovebox isolation technology in addition to a cleanroom. For easier comparison of analytical

results through time, we have converted all historical analytical results to the same units of measure.

However, we have not included test data that have been widely published or material tests not specifically

related to today’s cleanrooms and gloveboxes. While the intention of this report is to give a

comprehensive overview of the current state of organic cleanliness in JSC curation laboratories, it also

provides a baseline for determining whether our cleaning procedures and sample handling protocols need

to be adapted and/or augmented to meet the new requirements for future human spaceflight and robotic

sample return missions.

4

2.0 HISTORICAL ORGANIC CONTAMINATION RECORDS

2.1 Apollo Program and the Lunar Receiving Laboratory

NASA’s first astromaterials curation collection was lunar rock and soil samples returned to Earth by the

Apollo program in 1969. As early as February 1964, a Manned Spacecraft Center (MSC) internal memo

written by the Assistant Chief for Space Environment to the Director of Engineering and Development

identified the need for a Lunar Receiving Laboratory (LRL) and directed the concept of a 10’x10’x7’

vacuum chamber operating at 10-5

torr with remote manipulators for handling lunar samples. A vacuum

isolation chamber, rather than a positive pressure gaseous nitrogen chamber, was thought to be required to

preserve the lunar volatiles for sample analysis. In addition, scientists were concerned with sample

reactivity with Earth’s atmosphere. By March 1965, the Center for Disease Control (CDC) published

recommended procedures for Apollo sample handling and quarantine (Wood et al. 2002). In July 1965,

NASA and the U.S. Public Health Service recommended construction of the LRL to have adequate

biological barriers for both astronauts and returned samples. By January 1966, the Interagency

Committee on Back Contamination (ICBC) was consequently established to include the CDC with Dr.

David Sencer of the CDC as chairman, Department of Agriculture, Department of the Interior,

Department of Health, Education, and Welfare, National Academy of Sciences, and NASA (Mangus and

Larsen 2004). NASA’s Planetology subcommittee of the Space Sciences Steering committee formed the

LRL Working Group in May 1966 (Wood et al. 2002). The LRL Working Group and ICBC established

the final design of the LRL facility (MSC building 37) in September 1967 for biological quarantine of

astronauts, flown hardware, and lunar geologic material. After the establishment of the LRL, the Lunar

Sample Analysis Planning Team (LSAPT) and the Lunar Sample Preliminary Examination Team

(LSPET) were established to plan the handling and analysis of Apollo samples (Wood et al. 2002).

Scientists planning to work with lunar material designed a series of sample isolation chambers inside the

LRL biological barrier called the “high vacuum complex” that held a 10-6

torr vacuum environment

(White 1976) (figure 1). At the core of the high vacuum complex was the F-201 – a vacuum glove

chamber designed for initial sample processing (figure 2). In the late 1960s, glovebox isolation

technology was widely used by the nuclear and biological industry. The F-201 glovebox design was

based on technology directly derived from handling nuclear material at Oak Ridge National Laboratory

and would be used for preliminary sample examination. Materials for constructing the high vacuum

complex were chosen with emphasis on reducing organic contaminates. This included stainless steel,

Teflon - tetrafluoroethylene (TFE; C2F4), aluminum, Viton (fluorinated hydrocarbon), Pyrex glass for

windows, and molydisulfide (MoS2) lubricant. MoS2 is usually added to synthetic ester/fatty acid amides

to produce a grease applied to metal fasteners, and this compound was later determined to be a

contaminant. The F-201 glove assembly arm consisted of stainless steel lined with polyurethane (White

1976). The glove assembly fingers, thumb, and part of the hand were fabricated out of nylon and the

fingertips were impregnated with polyurethane. Viton A over-gloves were then used for each glove

assembly arm and hand; exposing only Viton A material to the inside of the F-201 chamber. The over-

gloves attached to the inner wall of the glove chamber and the glove assembly attached to a 10.5”

diameter Viton A O-ring flange that created an air-tight seal (White 1976). For cabinet sterilization, both

heat and peracetic acid sterilization was used in the atmospheric decontamination (R) cabinets of the

complex (figure 3). The vacuum complex design also used liquid nitrogen (LN2) cold traps that were

installed to reduce vacuum oil and other organic contamination. Further information on the design of the

F-201 and the high vacuum complex was written by David White in NASA technical Note D-8298

5

(August 1976) entitled, “Apollo Experience Report – Lunar Sample Processing in the Lunar Receiving

Laboratory High Vacuum Complex” (White 1976).

Figure 1: High Vacuum Complex during construction of the Lunar Receiving

Laboratory in 1968 (NASA Photo # S68-25212).

Figure 2: Components of the High Vacuum Complex in the Lunar Receiving

Laboratory (White 1976:3).

6

Figure 3: R-cabinets (Atmospheric Decontamination Cabinets) during construction

of the High Vacuum Complex in 1968 (NASA Photo # S68-25204).

The first analyses of organics in Apollo materials were completed by the Organic Gas Analysis Group

and the Action Committee on Organic Contamination. After the Apollo 11 mission, D.A. Flory of NASA

Manned Spacecraft Center, and B.R. Simoneit and D.H. Smith of Space Sciences Laboratory, University

of California, Berkeley submitted an unpublished report entitled the “Apollo 11 Organic Contamination

History” (Flory et al. 1969) to the Organic Gas Analysis Group and the Action Committee on Organic

Contamination. In May 1971, Simoneit and Flory wrote a full comprehensive report on organic

contamination in a Lunar and Earth Science Division Internal Note MSC-04350 entitled “Apollo 11, 12,

and 13 Organic Contamination Monitoring History” (Simoneit and Flory 1971). This document included

results and discussions about potential surface contamination of Apollo materials from a wide variety of

possible mechanisms. These include contaminants arising from the Apollo Lunar Sample Return

Container (ALSRC) and contents, Apollo Lunar Hand Tools (ALHT), exhaust products from the Lunar

Module (LM) (LM outgassing, venting of tanks, and Primary Life Support System (PLSS)), astronauts

suit leakage, astronaut suit abrasion, all miscellaneous samples, cleaning at the White Sands Test Facility

(WSTF), and contamination monitoring at the LRL. Flory and Simoneit (1972) also published their

findings from this report in Space Life Sciences on “Terrestrial Organic Contamination in Apollo Lunar

Samples” that has served the scientific community for years in understanding terrestrial organic

contamination on Apollo Lunar Samples. The JSC organic baseline contamination study will focus on

these historical reports concerning curation contamination analysis. We will highlight the Apollo 11 and

12 organic studies that involved the LRL and high vacuum complex contamination monitoring (Flory et

al. 1969; Simoneit and Flory 1971; Flory and Simoneit 1972; Simoneit et al. 1973). This will include

information from the March and June 1969 simulations, F-201 high-resolution mass spectral analyses, J-

Traps, LRL Ottawa sand organic monitors, and LRL and WSTF tool cleaning.

7

2.1.1 Lunar Receiving Laboratory Simulations and Cold Trap Analyses Apollo sample curation procedures were quickly developed, practiced, and refined prior to Apollo 11

sample return on July 24, 1969. JSC curation performed a rigorous cleaning procedure before simulating

the receipt of Apollo 11 samples and conducting organic contamination monitoring in the LRL high

vacuum complex. “Procedure for Cleaning the Sample Processing Complex (F-201)”, which was

designated CP-3, was used to reduce organic contamination from June 19, 1969 (Simoneit and Flory

1971). This procedure was also applied to the cleaning of the F-201, F-123, F-207, F-202, F-206, F-302,

and F-203 components of the high vacuum complex (figure 2). The following is a condensed version of

this procedure:

Vacuum interior with stainless steel or Teflon attachments

Wipe down with lint-free KimWipes and ethyl alcohol (190 proof)

Prepare complex for bakeout: open and close several series of valves, install cold panels, and

fill LN2 cold traps

Bakeout heat sterilization at 130°C ± 5°C for 48 hours

Cool complex to 50°C and backfill with nitrogen

Secure LN2 flow to cold traps; clean cold traps and seals with benzene/methanol solution

The CP-3 procedure relied heavily on the vacuum complex cold trap design to reduce organic

contamination. A residual gas analyzer was used to check cleanliness during the cleaning and visual

inspection. Due to higher-than-desired contamination levels found during Apollo 11 F-201 organic

monitoring, a CP-3 revision A was implemented in preparation for Apollo 12 (Simoneit and Flory 1971).

A written version of CP-3 revision A is dated to March 26, 1970, directly before Apollo 13 (Simoneit and

Flory 1971). The procedural revision of CP-3 replaced the use of ethyl alcohol with redistilled precision

cleaning agent (PCA) grade Freon 113 and added the use of dry, sterile nitrogen for drying the cabinets

before conducting the 130°C bakeout:

Vacuum interior with stainless steel or Teflon attachments

Wipe down with lint-free KimWipes and PCA Freon 113

Dry with sterile gaseous nitrogen (GN2)

Prepare complex for bakeout: open and close several series of valves, install cold panels, and

fill LN2 cold traps.

Bakeout heat sterilization at 130°C ± 5°C for 48 hours

Cool complex to 50°C and backfill with nitrogen

Secure LN2 flow to cold traps; clean with benzene/methanol solution

Two simulations were conducted in the high vacuum complex before Apollo 11 samples returned to

Earth. A series of test samples were analyzed to monitor organic cleanliness during the sample handling

process utilized in F-201. The samples were tested at both the University of California Berkley – Space

Science Laboratory (UCB-SSL) and the Gas Analysis Laboratory (GAL) at the MSC LRL. The March

1969 simulation reported the first contamination results from a sample for the Burlingame-Biemann

experiment. A fired "Chromosorb-X" sample in a stainless steel container was introduced into F-201

under vacuum. The Chromosorb-X sample was transferred to aluminum foil inside the F-201 using the

glovebox gloves. The sample was then placed into a nickel container through a Teflon funnel and the

container was then analyzed in the GAL. According to the laboratory notes, the container and funnel

8

were exposed to contamination on the glovebox floor surface of the F-201. The experimental results

report a relatively large amount of organic contaminants with silicone oil being the largest component.

Silicone grease was predominately used for sealing flanges in the high vacuum complex including the O-

ring flanges on the F-201 glovebox gloves. The March 1969 simulation was the first indication that the

cold traps were not effectively removing all the silicone oil and other organic contaminants from the high

vacuum complex. The Simoneit and Flory (1971) report also mentions that the silicone oil would prove

to be very difficult to remove once it was introduced into the vacuum system.

Sample handling simulations continued in order to further reduce contamination. In the June 1969

simulation, five samples were run on the Organic Gas Analysis (OGA) Experiment, namely simulation

(SIM) samples 2, 3, 4, 5, and 6. SIM sample 2 was a chromosorb sample supplied by F. Woller at NASA

Ames Research Center (ARC) that was exposed to F-201 and a rock box. The analysis spectra indicated

unsaturated hydrocarbons, with the highest observed peaks at a mass to charge ratio for the ion, m/e = 103

– 105 with 7.34 X 104 ion current/mg. SIM sample 5 was the control blank for SIM 2 run through the

GAL. A major peak was found at m/e = 18, 47% of the total ion current. The total yield was found to be

1.59 X 104 ion current/mg, a factor of 4.6 below the F-201 sample. SIM sample 3 was a quartz sample

tube that had a relatively high ion current of 7.02 X 105

ion current/mg. However, it was noted that there

was a manufacturing defect with the sample tube. SIM sample 4 was a quartz sample tube that was

placed in an indium sealed container. The container was transferred to the F-201 through a glove port and

exposed for 4 days before the simulation. SIM 4 produced a mixture of unsaturated hydrocarbons, as

noted in the chromosorb spectra with peaks to about m/e = 300. The second highest peaks were at m/e =

55 and lesser peaks up to m/e = 130. The third highest peaks range from m/e = 50 – 57. The team

interpreted some of the spectra as benzene from the cleaning procedure. The total yield resulted in 1.38 X

105 ion current/mg. SIM sample 6 was a quartz blank from the Physical Chemistry test area. The total

yield was 4.1 X 103 ion current/mg, a factor of 34 below the F-201 exposed sample. The report notes that

another experiment was run by summarizing the quartz sample data with all masses above m/e = 50. This

resulted with the blank at 3.7 X 102 ion current/mg and the F-201 at 5.56 X 10

4 ion current/mg. This was

a factor of 165 more total ionization above m/e = 50 for the F-201 exposed sample.

Prior to the return of Apollo 11, high-resolution mass spectral analyses were also conducted on the F-201

vacuum system Granville-Phillips cold trap to identify organic contamination. Rinse residue from the

CP-3 (1969 version) F-201 cleaning procedure was analyzed by gas liquid chromatography and high-

resolution mass spectrometry (GLC-MS). The GLC-MS analyses were run on a Varian-Aerograph Model

204 gas chromatograph or a Perkin-Elmer Model 900 gas chromatograph with packed columns and GEC-

AEI MS-902 mass spectrometer online to an XDS Sigma-7 computer. The mass spectra showed large

amounts of octoil (dioctyl phthalate (DOP) plasticizer) and hydrocarbons through C30, predominantly

through C24. Several molecular compounds containing one oxygen atom were found, mostly C19H32O

(androstanol) and C19H28O (androstenone, predominantly found in sweat and urine). The interpretation at

the time was that these compounds were possibly steroidal in nature due to the degree of unsaturation.

The F-201 LN2 cryogenic cold trap was tested for organic contamination after subsequent 120°C

sterilization of the vacuum system. Rinse residue from the washings was again analyzed by GLC-MS.

This residue was much more complex in nature compared to the Granville-Phillips cold trap with many

different classes of compounds represented. The major compounds included octoil (dioctyl phthalate

(DOP)), tri-n-butyl phosphate (TBP) – organophosphorus compound, a plasticizer, and hydrocarbons

through C33, predominantly unsaturated. An unknown silicone oil/grease used for the vacuum glove seals

9

was also found in large quantities in the F-201. Several unidentified organic chemicals related to silicone

oils/grease were found on a fired Chromosorb X after the March 1969 simulation and is explained in

more detail in the "Supplementary Report to G. Eglinton’s Report to LSAPT on Organic Contamination

Problems," April 17, 1969, by A.L. Burlingame and D.H. Smith, Space Sciences Laboratory, University

of California, Berkeley. The minor components were C16 – C18 free acids and di-n-butyl decanedioate,

C4H9OGO(CH2)8COOC4H9 (dibutyl ester). The sebacic acids (naturally occurring dicarboxylic acid) are

used in formulation of alkyd resins, and their esters are typically used as plasticizers, paint, hydraulic

fluids, and synthetic lubricants. The silicone oils and plasticizers were found to be present even after

multiple cleanings of the F-201. Today, it is hypothesized that the molydisulfide lubricant used

throughout the high vacuum complex contributed to this silicone oil contamination (Charles Meyer, pers.

comm. 2012). The results from the cold panel cryotrap were also noted to have major components of

dibutyl phthalate, dioctyl phthalate, and decanedioate esters and minor components of cyclohexanone and

other oxygenated fragments, unsaturated hydrocarbons < C20, and carboxylic acids.

The cold finger J-Traps (J-101, J-124, and J-125) during bakeout for Apollo 11 were also analyzed by

GLC-MS. J-101 resulted in the identification of dioctyl phthalate, hydrocarbons < C18 (possible

hydrocarbon oils) and carboxylic acids < C7. J-124 resulted in major components of C4H8O2, m/e = 88,

C2H4O2 m/e = 60, M-CH3, m/e = 73; and M-OH m/e = 71 mixture with butyric acid. In addition, dibutyl

phthalate, as was reported for F-201, and dioctyl phthalate were also found. The J-125 had similar result

to J-124 with a higher dioctyl phthalate peak.

2.1.2 Lunar Receiving Laboratory Ottawa Sand Organic Monitors

Ottawa sand organic monitors (OMs) were developed to monitor background contamination levels in the

LRL processing cabinets. Two batches of standard Ottawa sand was sieved to 20-30 mesh for the F-201

vacuum system and for “bioprep” nitrogen processing cabinets. The F-201 system sand was washed with

water and baked at 1000°C overnight. The bioprep batch was prepared with an acid washing reagent and

baked at 1000°C for 30 hours at ARC. Control analyses of the batches used a benzene/methanol

extraction and high-resolution mass spectrometry at UCB-SSL and the pyrolysis-mass spectrometer at the

LRL. The F-201 OM control resulted in 3.08 μg/g of adsorbed organics with a calculated 136 ng/cm2.

The bioprep OM sand control generated 2.32 μg/g of adsorbed organics with a calculated 103 ng/cm2.

The spectral data shows mainly hydrocarbons from C4 to C25 and dioctyl phthalate. Minor amounts of

oxygenated species (such as cyclic ketones and carboxylic acids), and unknown C23H32O2 and C13H12O2

species were also found. Two Ottawa sand monitor backgrounds were established for the curator sample

packaging clean cabinet that had adsorbed organics of 3.75 μg/g with a calculated 170 ng/cm2 and 6.3

μg/g with a calculated 280 ng/cm2. The GLC spectra also showed traces of dioctyl phthalate and some

other lower weight organics.

Background monitoring for Apollo 11 was done with Ottawa sand in the LRL GAL and corrected with

the OM controls. Samples were labeled as “BL” (Blank) with a corresponding sample number in some

cases. Figure 4 shows the complied results from Simoneit and Flory (1971) report.

10

Figure 4: LRL Apollo 11 Ottawa sand organic monitoring results (Simoneit and Flory 1971).

In the Simoneit and Flory (1971) report, BL 03 was considered a “good blank” for the bioprep cabinetry

atmosphere with an estimated organic contamination level of 17.2 ng/cm2

(<1 ppm) along with 13.7

ng/cm2

(<0.5 ppm) for BL 04. The BL 03 sample consisted mainly of volatile hydrocarbons and some

formaldehyde residue. The sample also had traces of silicone oil, Teflon, indium, and lead. The F-207/F-

201 sample was also low with 7.8 ng/cm2 estimated organic contamination for BL 05. The F-201 BL 06

sample was heavily contaminated with hydrocarbons from turbo pump oil and an unknown source of

chlorinated diphenyls.

The Apollo 11 organic monitoring also sampled a WSTF cleaning blank (sample number 1006) and Ni

capsule blanks. The WSTF OM resulted in 30 ng/cm2 surface contamination. The major product of the

contamination was from solvents such as Freon and benzene. A Ni capsule blank (sample number 1009)

resulted in 6 x 105

ion current/mg with a calculated organic contamination level of 1.2 ng/cm2. The GAL

Ni capsule blank (sample number 1016) resulted in no significant organic material evolved from the

capsule. The total ionization was 7.6 x 105 ion current/mg with an estimated organic contamination level

of 1.5 ng/cm2. The peracetic acid used at the LRL for sterilization was also analyzed for residual films by

Dr. Rainer Berger (UCLA). After procedural deionized water washing, the organic residue extractable with

3:1 benzene/methanol was found to range from 1 to 10 μg/cm2. It was also reported that the first

benzene/methanol extract after the water washing reduces the organic contamination level by a factor of 5 to 7.

Sample Sample Type

LRL

Location

Exposure

Time ion current/mg

Estimated

Organic

Contamination

Level (ng/cm2 )

BL01 (#1007)

Ottawa Sand

Blank in an

outgassed Ni

capsule

BioPrep

Cabinetry 2.1 hours 6.35 X 105

240

BL02 (#1008)

Ottawa Sand

Blank in an

outgassed Ni

capsule

BioPrep

Cabinetry 2.1 hours 7.0 X 105

230

BL03 (#1010)

Ottawa Sand

Blank transferred

from glass

ampoule to an

outgassed Ni

capsule

BioPrep

Cabinetry 30 min. 6.3 x 106

17.2

BL04 (#1011)

Ottawa Sand

Blank transferred

from glass

ampoule to an

outgassed Ni

capsule

BioPrep

Cabinetry 3.5 hours 9.3 x 106

13.7

BL05 (#1014)

Empty Ni Capsule

cleaned at WSTF,

baked in F-201 at

120°C for 12

hours F-207

Sample

processing 4.1 x 106

7.8

BL06 (#1015)

Ottawa Sand

Blank in an

outgassed Ni

capsule F-201 20 days 1.3 x 108

490

LRL Apollo 11 Organic Monitors

11

Apollo 12 background organic monitoring was also conducted in the GAL in the LRL. Based on the results

from the organic monitoring during Apollo 11, the F cabinet cleaning procedure CP-3 was improved with

revision A and resulted in reducing the overall organic load with the introduction of Freon 113. The figure

below shows the complied Apollo 12 OM results from the Simoneit and Flory (1971) report.

Figure 5: LRL Apollo 12 Ottawa sand organic monitoring results (Simoneit and Flory 1971).

BL 08 sample was exposed to the bioprep cabinet for 5 hours with an observed 5.2 x 10

5 ion current/mg

and a calculated organic content of 0.6 ng/cm2 (<0.1 ppm). The BL 07 Ames Ottawa Sand monitor was

the control monitor for BL 08 and had an observed 3.3 x 105 ion current/mg with a calculated organic

content of 0.7 ng/cm2 (<0.1 ppm). BL 15 was an Ottawa Sand organic monitor with exposure to the

bioprep cabinetry for 48 hours. The result was 6.9 x 106 ion current/mg with a calculated organic load of

40 ng/cm2. This analysis also highlighted the detection of decomposition products of some Teflon

contamination, as well as volatile hydrocarbon contamination. BL 16 was the bioprep Ottawa Sand OM

control that resulted in 1.9 x 106 current/mg with an estimated organic load of 12 ng/cm

2. BL 17 was an

empty sample capsule from the previous analyses that was reinserted after sand removal. The results

reported 5.0 x 105 current/mg with an estimated organic load of 2 ng/cm

2.

BL 11 F-201 Ottawa Sand was exposed to the F-201 vacuum chamber for 11 days with nitrogen

backfilled three times for a total of 60 hours under nitrogen. This resulted in 2.3 x 106 ion current/mg

with a calculated organic content of 1.7 ng/cm2 (<0.1 ppm). The F-201 control was BL 10 Ottawa Sand.

The sample had an observed 1.5 x 106 ion current/mg with an estimated organic content of 1.5 ng/cm

2

(<0.1 ppm). BL 12 was a solvent background for BL 07 resulting in 0.1 x 106 ion current/mg with an

estimated 0.04 ppm organic content. BL 13 and 14 were run as calibration tests. BL 13 experienced

some sample insertion problems and BL 14 was the rerun background monitor. BL 14 resulted in 2.38 x

106 ion current/mg.

For Apollo 13, the cabinets were cleaned again with CP-3 revision A and the formal procedure was

written on March 26, 1970. The CP-12 procedure, dated March 26, 1970, was established for sampling

and counting air particles in the LRL clean rooms, clean workstations, or controlled work areas. The

procedure was the first detailed process for microscopic particle counting on work surfaces and

gloveboxes and is the progenitor for similar, modern-day cleanroom processes. Unfortunately, no

simulations or organic monitors were conducted for Apollo 13. The Simoneit and Flory (1971) report

suggest that this was due to changes in personnel in the LRL and waiting on the success of Apollo 13.

Sample Sample Type

LRL

Location

Exposure

Time ion current/mg

Estimated

Organic

Contamination

Level (ng/cm2 )

BL07

Ames Ottawa

Sand

BioPrep

Cabinetry

BioPrep

Control 3.3 X 105

0.7

BL08

Ames Ottawa

Sand

BioPrep

Cabinetry 5 hours 5.2 X 105

0.6

BL15

Ames Ottawa

Sand

BioPrep

Cabinetry 48 days 6.9 X 106

40

BL10 LRL Ottawa Sand F-201 F-201 Control 1.5 X 106

1.5

BL11 LRL Ottawa Sand F-201 11 days 2.3 X 106

1.7

LRL Apollo 12 Organic Monitors

12

2.1.3 Lunar Receiving Laboratory and White Sands Test Facility Tool Cleaning The LRL cabinet tools were originally cleaned with a special LRL “flush and wipe” procedure. The

procedure used lint-free KimWipes and Freon 113 to wipe or flush the tools along with a final rinse with

Freon 113. Tool cleanliness was verified by a series of Total Organic Carbon (TOC) analyses that were

run by GLC in the GAL. The first TOC analyses from a Freon blank, Gas Reaction Cell, and Gas

Sampling Probe resulted in 200 ppm (mg/L) of organic contamination. The 200 ppm TOC levels were

found to be too high for curation use, possibly due to the Freon distillation equipment installed at NASA

MSC. Therefore, modified cleaning procedures sent all sample containers except the radiation counting

lab (RCL) containers to WSTF for cleaning. For emergency situations, any tools that were not cleaned at

WSTF could be cleaned at the LRL by a procedure outlined by the Organic Contamination Control

Officer, entitled "Contingency Cleaning Procedure for LRL Apollo 11 Lunar Processing Tools." The

following is a condensed version of this procedure for cleaning stainless steel, aluminum, and Teflon:

Preclean:

5 min. immersion in PCA Freon 113

5 min. ultrasonication in 1% Alconox detergent solution

Rinse with tap water

Rinse with deionized (DI) water

Rinse with isopropyl alcohol (IPA)

Dry with filtered dry sterile nitrogen

Final Clean in Class 100 Cleanroom:

5 min. ultrasonication in PCA Freon 113 with Bendix ultrasonic degreaser

Spray rinse in PCA Freon 113

Collect spray rinse sample for particle counts, Non Volatile Residue (NVR), and TOC

analysis in LRL GAL

The condensed procedure for Viton cleaning was the following:

Preclean:

Flush with cold tap water

10 min. immersion in 150°F Oakite Liqui-Det #2 (1 oz. to 1 gal. water) detergent solution

assisted with nylon brushes

Rinse with hot tap water (max. 140°F)

Rinse with DI water

Dry with filtered dry sterile nitrogen

Final Clean in Class 100 Cleanroom:

1 min. spray rinse with PCA Freon 113

Collect spray rinse sample for particle counts only

The revised Contingency Cleaning Procedure for LRL Apollo 11 Lunar Processing Tools resulted in TOC

Freon blanks of 0.08 ppm (mg/L), much lower than with the special LRL “flush and wipe” procedure.

TOC analyses with this new contingency cleaning procedure for LRL tools and parts ranged from 0.02 to

13

5.24 ppm (mg/L) (Simoneit and Flory 1971). At WSTF, the majority of LRL tools were cleaned by CP-7

(Revision A) “Procedure for Cleaning Tools and Equipment used in the Vacuum Laboratory Processing

Complex”, dated September 24, 1969, and March 26, 1970. The following is a condensed version of this

procedure:

Preclean:

10 min. immersion in PCA Freon 113

5 min. ultrasonicate in 1% Alconox detergent solution

Rinse with tap water

Rinse with DI water

Rinse with chemically pure (CP) IPA

Dry with filtered dry sterile nitrogen (GN2)

Final Clean:

10 min. immersion in 3:1 benzene/methanol solution, reagent grade

30 sec. immersion in PCA Freon 113

15 sec. spray rinse with PCA Freon 113

Air dry

Class 100 Cleanroom Clean:

5 min. ultrasonicate in PCA Freon 113

Spray rinse with PCA Freon 113

Placed parts in clean Teflon bags purged with GN2

Samples were also collected during the final Freon ultrasonication bath and spray rinse for particle counts,

Non Volatile Residue (NVR), and TOC analysis. “Procedure for Cleaning Plastic and /or Rubber Tools

or Equipment for Use in LRL”, designated CP-5, dated August 1, 1969, was also used at WSTF. The

following is a condensed version of this procedure:

5 min. ultrasonication with 1% Alconox cleaning solution

Rinse with tap water

Rinse with DI water

At a Class 100 workstation, Rinse with 190 proof ethyl alcohol

Run TOC analysis

CP-5 revision A, March 26, 1970

5 min. ultrasonication with 1% Alconox cleaning solution

Rinse with DI water at 140° F

Rinse with filtered DI water

Take particle counts

Air dry for 1 hour and package in Teflon

For Viton over gloves, wipe down with KimWipes and 190-proof ethyl alcohol

14

The WSTF LRL tool organic analyses from CP-7 and CP-5 cleaning procedures showed the level of

organic cleanliness to be between 0.5 to 1.0 ng/cm2 and were thought at the time to be well within

specifications for most tools. However, the WSTF high-resolution mass spectral analyses showed

evidence of dioctyl phthalate, phthalate esters, carboxylic acids, and traces of hydrocarbons.

ALSRCs were designed to preserve samples in a lunar-like vacuum. A York mesh lining, knitted from

2024 aluminum alloy, inside the ALSRC was used to protect the samples from vibration and shock during

return flight. Analyses of aluminum foil and York mesh samples from the Apollo 11 mission indicated

organic contamination levels of about 1 µg/cm2. Paradoxically, Apollo 11 bakeout of the ALSRCs in the

LRL actually resulted in adding organic contamination. These organic monitoring results led to

improvement in flight hardware for Apollo 12 and future missions and resulted in about 10-100 ng/cm2 of

organic contamination. For the York mesh material, a 100 ng/cm2 cleanliness level was the lowest

achieved. This was possibly due to aluminum oxide residues and high adsorption characteristics of the

material.

Outgassing of Apollo spacecraft, spacesuit, equipment, et cetera introduced no detectable contamination

to the lunar samples from Apollo 11 and 12. However, LM engine exhaust products were seen in the

samples. The exhaust products were minor in concentration, but can be seen over large areas. Organic

compounds consisted of acetylene, hydrogen cyanide, ethylene, formaldehyde, propadiene, ketene,

cyanous acid, hydrazoic acid, various methyl amines, acetaldehyde, methyl nitrite, formic acid, nitrous

acid, butadiyne, various hydrazines, nitromethane and some nitrosohydrazines with traces of other

oxidation derivatives of UDMH and hydrazine. For the bulk sample box, organic contamination levels

were calculated to be 2.5 x 10-10

g/g for LM contamination.

2.1.4 Lunar Receiving Laboratory Organic Results Summary

Lunar samples placed into the F-201 glovebox were mostly contaminated by large amounts of octoil (i.e.,

DOP) and hydrocarbons predominantly through C24 (Flory et al. 1969; Simoneit and Flory 1971). Tri-n-

butyl phosphate and di-n-butyl decanedioate were also found in significant quantities. The unknown

silicone oils (mostly likely from the use of molydisulfide lubricant) were also present, but in much lower

concentrations. The June 1969 simulation analyses found large amounts of contamination due to

unsaturated hydrocarbons. However, hydrocarbon contamination was largely absent from the R cabinetry

blanks even though these samples documented a peracetic acid leak. R cabinetry (R-101, R-102, R-103)

were the atmospheric decontamination “airlocks” attached to the vacuum system (figures 2 and 3).

Particulate contamination was also observed during both Apollo 11 and 12 during LRL preliminary

examination by the Preliminary Examination Team (PET). It was noted that, in one case, small fragments

of gold-coated Mylar insulation was found from the LM. Teflon particles from the sample bags were also

found on the samples. Figure 6 is the compiled summary list of LRL organic contaminates (Flory and

Simoneit 1972; Simoneit and Flory 1971; Simoneit et al. 1973).

15

Figure 6: Compilation of known LRL organic contaminants (Flory and Simoneit 1972;

Simoneit et al. 1973; Simoneit and Flory 1971).

The Apollo program organic contamination summary described the desire to reduce potential

contamination to below 1 ng/g (Flory et al. 1969; Simoneit and Flory 1971; Simoneit et al. 1973). It also

desired the development of cleaning protocols capable of reducing organic contamination below 1 ng/cm2

on surfaces (Simoneit and Flory 1971; Flory and Simoneit 1972). In most cases, cleaning for bright,

polished, planar surfaces resulted in cleanliness levels in the range of 1 to 10 ng/cm2. From the point of

sample collection with the ALSRC to scientific distribution of sample from the LRL, the report highlights

several potential significant sources of organic contamination. For the LRL, prior to Apollo 11, organic

contamination levels were observed as high as 1000 ppm, and could potentially be introduced to lunar

samples. Revamping laboratory sample handling and cleaning procedures reduced this level of organic

contamination to < 1 ppm for the Apollo 11 samples (Flory and Simoneit 1972; Simoneit et al. 1973).

Further procedural revisions based on organic monitors and careful analysis of contamination sources,

reduced organic contamination levels even further to below 0.1 ppm during Apollo 12 and later missions.

In many cases, this was below the level of contamination in organic geochemistry research laboratories at

the time.

Organic Compounds LRL Location

Hydrocarbons Ubiquitous

Fatty AcIds F-201 (LRL High Vacuum Complex Processing)

Palmitic Add F-201 (LRL High Vacuum Complex Processing)

Stearic Acid F-201 (LRL High Vacuum Complex Processing)

Dibutyl Phthalate F-201

Dioctyl Phthalate Ubiquitous

Didecyl Phthalate Apollo Lunar Sample return Container (ALSRC)

Dinonyl Phthalate Apollo Lunar Sample return Container (ALSRC)

Dioctadecyl Phthalate Apollo Lunar Sample return Container (ALSRC)

Silicones F-201, Astronaut suit

Trimethylene oxide Nitrogen Sample Processing cabinet

P-Dioxane Nitrogen Sample Processing cabinet

1,3,5,-Trimethyl-2,4,6 -Trioxane Nitrogen Sample Processing cabinet

Orcinol Nitrogen Sample Processing cabinet

Freons NASA WSTF Cleaning

Tributyl Phosphate F-201

Trihexyl Phosphate ALSRC

Oleamide ALSRC

Cholesterol ALSRC

Dibutylsebacate F-201

Dioctyladipate SESC Lid (Apollo 12)

Chlorodiphenyls ALSRC

Diisopropyldisulfide ALSRC

Pyrene F-201

Tetrahydronaphthol ALSRC

Ionol polypropylene bottles

Teflon Nitrogen Sample Processing cabinet

16

The LRL facility organic monitoring results are the most comparable data with today’s curation

cleanrooms and gloveboxes (figures 4 and 5). In the late 1960s, gas chromatographic and mass

spectrometry techniques used in organic geochemical and bioscience investigations were capable of

detecting organic compounds in quantities < 1 ng/g (ppb) (Simoneit and Flory 1971 and Flory and

Simoneit 1972). As a comparison, today’s gas chromatography mass spectroscopy instruments are

capable of detecting organic compounds in quantities < 0.1 ng/g (ppb), an order of magnitude lower, with

limits of detection of mass per volume approaching < 20 fg/ml (ppq) (Fialkov et al. 2007).

2.1.5 Lunar Receiving Laboratory Biological Containment

In addition to geologic preliminary examination in the high vacuum complex, a subset of lunar samples

were required to be examined by biologists in separate laboratories inside the biological barrier in the

LRL building 37. Lunar samples were placed inside a series of class III biological containment

gloveboxes to evaluate the risk of biological pathogens and other signs of back contamination. The class

III biological glovebox technology was based on biosafety level 4 isolation technology derived from

handling the most extreme pathogens at Fort Detrick. However, little is known about the manufacturer of

these Class III gloveboxes and any organic contamination testing that may have been done prior to the

arrival of samples. Lunar samples were initially processed in the F-201 glovebox simultaneously with the

quarantine period. The biological safety tests were derived from the Comprehensive Biological Protocol

for the Lunar Receiving Laboratory (Baylor University College of Medicine 1967). The Baylor

University College of Medicine developed the “Baylor Protocol,” which was a series of biological tests of

lunar material. The Baylor Protocol included tests of bacteriology, mycology, virology mycoplasma,

mammalian animals, botanical systems, and invertebrate/lower vertebrate systems. However, the full

procedure was never fully implemented. The biological quarantine of the Apollo program in the LRL is

well documented. Suggested further reading includes: Mangus and Larsen 2004; McLane et al. 1967;

Allton et al. 1998; Benschoter et al. 1970; Eglinton et al. 1974; Fox et al. 1981; Gehrke et al. 1971, 1972,

1975; Harada et al. 1971; Holland et al. 1973; Johnson et al. 1972; Kemmerer et al. 1969; Long et al.

1972; Sagan 1972; Taylor et al. 1970, 1971, 1973; Walkinshaw et al. 1970, 1973; Weete and Walkinshaw

1972. The final conclusion of these studies stated that all soluble organic compounds and amino acids

found in the samples were indigenous to Earth. The lunar sample quarantine testing concluded that there

was no evidence of life or any biological hazard to impede the release and distribution of samples for

scientific research outside the LRL biological barrier. After the Apollo 14 mission, all quarantine

protocols were abandoned and only a few fundamental carbon studies were done on later missions

(Mangus and Larsen 2004). In addition to the biological studies, several published studies on carbon, C

isotopes, carbon monoxide, methane, carbon dioxide, and hydrocarbons found in lunar material are

available and suggested readings include: Abell et al. 1971; Burlingame et al. 1970; Cadogan et al. 1971,

1972; Chang et al. 1971; Epstein and Taylor 1970, 1973; Friedman et al. 1970; Holland et al. 1972;

Kaplan and Smith 1970; Kaplan et al. 1970; Kvenvolden 1972; Moore et al. 1970; Nagy et al. 1970,

1971; Oró et al. 1970, 1971.

High vacuum is intrinsically difficult to work with, especially when manipulating large numbers of

samples. As a result, the F-201 and other components in the high vacuum complex were prone to leaks

and glove failure. After Apollo 12, high vacuum was replaced with gaseous nitrogen gloveboxes based

on biological isolation cabinet designs. In November 1970, just before Apollo 14 return samples, the

LSAPT deactivated F-201 and replaced it with a series of gloveboxes called the Sterile Nitrogen

Atmospheric Processing (SNAP) Line (figure 7) and Nonsterile Nitrogen Processing Line (NNPL) (Wood

17

et al. 2002). During Apollo 14, the SNAP line gloveboxes were used as the primary quarantine and were

set at 1.0 inH2O negative pressure with oxygen at 25 to 50 ppm and moisture restricted to 85 to 125 ppm

(Reynolds et al. 1973). The NNPL was used to process lunar material more quickly after the quarantine

period in the SNAP line. The NNPL was set at a slight positive pressure nitrogen environment with

oxygen at 10 to 30 ppm and moisture at 15 to 25 ppm (Reynolds et al. 1973). Flory and Simoneit (1972)

suggest that as much as 10 ppm of organic contamination was added by the introduction of the SNAP line

over the use of the high vacuum complex (Simoneit et al. 1973). The main source of organic

contamination was the sterilization process, which used ethylene oxide and created polymerization

products as well as introduced dioctyl phthalate.

After Apollo 14, the Apollo program quarantine requirements were abandoned. The LRL continued to

operate more as a curation laboratory than a quarantine facility for Apollo 15 through 17. In 1973, all

Class III biological gloveboxes and the high vacuum complex were abandoned and disassembled in favor

of the continued use of positive pressure GN2 environment gloveboxes. We have little documentation of

what happened to these LRL gloveboxes. However, Everett Gibson (pers. comm. 2012) suggest that the

F-201 glovebox and high vacuum complex was disassembled and relocated to Los Alamos National

Laboratory to be used for other government projects.

Figure 7: SNAP line in LRL during Apollo 14 in 1971 (NASA Photo # S-71-19264).

18

2.2 Establishing the Lunar Curation Laboratory 1973 to 1979 After Apollo, the LRL was replaced with a dedicated curation facility. From 1973 to 1979, an interim

lunar curation laboratory was established on the second floor of JSC building 31 (B31). Today, this area

houses the Antarctic Meteorite, Stardust, and Cosmic Dust laboratories. During this time, a plan was

initiated to expand B31 and construct a new facility called building 31 North (B31N). From 1970 to

1972, new GN2 gloveboxes were manufactured by Stainless Equipment Company in Englewood,

Colorado, and placed in the interim lunar laboratory in B31. In addition to planning B31N, NASA built a

remote storage facility for lunar samples at Brooks Air Force Base in San Antonio, Texas, in 1975. This

remote storage facility was designed to continuously house a subset of the lunar sample collection in case

of a catastrophic event in Houston. In 1979, B31N was established as the new lunar curation laboratory.

About 80%, by weight, of lunar samples still reside in this facility with a subset stored at a remote

location as well as samples allocated for scientific research and educational outreach. The B31N

gloveboxes were manufactured from 1977 to 1978 by the Stainless Equipment Company and were

designed with 316L stainless steel (11 and 14 gauge with continuous welds), 304 stainless steel pipe

fittings, Viton gaskets, safety glass windows, and neoprene gloves. It should be noted that the glove

material was not mentioned in Stainless Equipment Company primary documents, but these gloves are

used today and are thought to be the original choice in 1978. Most of the original glass windows cracked

early on and were replaced with Lexan (polycarbonate) material (Jack Warren and Charles Meyer pers.

comm. 2012). After an extensive data mining effort in the JSC curation data center, no primary

documentation or reports were found that detailed organic testing for the gloveboxes purchased from the

Stainless Equipment Company from 1970 to 1978. However, there are LSAPT facility subcommittee

minutes from May 1975 to March 1979 that document the construction of the B31N Lunar Laboratory as

well as Brooks Air Force Base remote storage. After Apollo 12, the Apollo program in 1970 began to

relax organic requirements for Apollo 13 and subsequent missions. This relaxation of requirements

seems to coincide with the LSAPT discussions that the scientific community no longer required

organically clean samples. However, facility construction memos and LSAPT meeting minutes do

suggest that material testing did occur after Apollo 12, but the role of organics was not thoroughly

explored. Some LSAPT memos suggest that these organic investigations may have been related to future

human spaceflight Mars mission planning in the early 1970s at the end of the Apollo program.

2.3 Xylan Contamination and Lessons Learned 1972 to 1990

Xylan is a lubricating polytetrafluoroethene (PTFE) Teflon paint coating manufactured by Whitford

Corporation in West Chester, Pennsylvania. In 1972, Xylan was proposed as a replacement for the

molydisulfide lubricant universally used on fasteners in the LRL. For about 18 years (1972 to 1990),

Xylan was primarily used in the Lunar and Meteorite laboratories for stainless steel fastener (screw and

bolt) threads. Xylan was used to prevent galling in lab jacks, bolt top sample containers, inside and

outside glovebox door handles, camera mounts, band saw stage, band saw blades, band saw screws, and

various core drive tube dissection hardware. The introduction of Xylan into the Lunar curation laboratory

was documented in a series of internal JSC memos in the early 1970s. A.H. Beatty, Jr. of Brown & Root

– Northrop first proposed on January 12, 1972 an evaluation and use of Xylan 1010 coating on bolts to

prevent stainless steel galling in the Lunar curation facility. The next day (January 13) Kenneth Suit in

the Laboratory Operations Branch requested that the Contamination Control Committee approve Xylan

1010 as an accepted material for use in the curation labs based on Beatty’s proposal. On January 25,

1972, the use of Xylan 1010 was conditionally approved by Michael Duke, chairman of the

Contamination Control Committee, with three constraints: 1) no pigment used in manufacturing; 2) 20

19

test coupons were requested for stainless steel and aluminum; and 3) the Whitiford Corporation must

submit all operating procedures related to manufacturing of Xylan. The Duke memo further stated that if

all three criteria were met, the contamination control committee would formally consider the material for

acceptance. The next day (January 26) Kenneth Suit wrote a memo delaying the proposed investigation

of Xylan due to the Apollo 16 schedule. On February 2, 1973, the Contamination Control Committee

chair, now Michael Reynolds, approved Xylan after receiving documentation from JSC and the Xylan

manufacturer. The memo also notes that JSC personnel visited the Whitford manufacturing plant in

Pennsylvania and provided the requested chemical information to the committee. However, it is unclear

from the available documentation whether all the constraints on Duke’s memo were met and completed.

The first written indication of possible Xylan contamination was documented in an internal routine memo

on October 22, 1986, by Charles Meyer, JSC Contamination Control Officer. Meyer mentions that JSC

scientist Dave McKay observed flakes of the Xylan material on the lunar core extrusion table during

sample processing. Meyer states that this warrants further investigation of Xylan contamination. On

December 1, 1986, Meyer wrote a memo to JSC Deputy Chief Biomedical Branch on the Xylan

offgassing analysis. The report discusses the real possibility that Xylan is contaminating the astromaterial

collections and should be removed from all curation labs (Lunar, Meteorite, and Cosmic Dust labs at the

time). This memo did not prompt the immediate removal of Xylan, to a certain extent, because no

adequate substitute was proposed to prevent thread galling and subsequent particle contamination.

Ian Wright et al. (1989) of The Open University in the United Kingdom (UK) published an article in the

July 20, 1989 issue of Nature entitled “Organic Materials in a Martian Meteorite.” This scientific team

claimed to have found the first chemical signatures of organic compounds from Mars. After internal

discussions of this publication and the possibility of JSC contamination affecting the results, Charles

Meyer wrote another memo about the contamination report on Xylan to the Lunar Sample Curator on

October 16, 1989 – almost 3 years later. The memo again discusses the possibility that Xylan was

contaminating astromaterial collections and should be removed from all curation labs. After little

response from the Lunar Sample Curator, on April 20, 1990, Meyer wrote a memo to the general curation

staff on the Xylan problem and potential for contamination. In addition, on May 21, 1990, Charles

Meyer, now Associate Curator, wrote another memo to the Lunar Sample Curator about the Xylan

problem. Meyer further reported and officially briefed curation on the February 1990 Lunar and

Planetary Science Team (LAPST) meeting discussion on Xylan contamination and the possibility of

causing a false positive chemical signature of organic compounds from the Martian meteorite.

On May 25, 1990, NASA LAPST chairmen Michael Drake and Lunar and Planetary Institute director

David Black wrote an official letter to NASA JSC Solar System Exploration Division Chief Michael

Duke. Duke was the chairman of the Contamination Control Committee who had requested additional

testing of Xylan before material approval in 1972. In the LAPST memo, Drake wrote that JSC curation

must cease all operational use of Xylan and eliminate Xylan contamination effective immediately. The

memo also stated that JSC curation must document all present and past usage of the material. From

February to June 1990, several curatorial orders were written by Meyer to investigate the extent of Xylan

use and to remove it from curation labs.

Based on this letter, Ruska Laboratories were contracted by JSC curation to conduct a complete analysis

of Xylan in May 1990. After testing, Xylan was found not to be a pure fluoropolymer but a combination

20

of multiple chemicals when applied as a liquid resin. The results showed that the chemical composition

of Xylan 1010 included the following:

Polytetrafluoroethylene (PTFE)

Fluorinated ethylene propylene (FEP)

Polyamide

Ethyl Acetate

N, N – Dimethylformamide (DMF)

Xylene

N-Methyl-2-pyrrolidone (NMP)

While the major components of Xylan were found to be a mixed fluoropolymer, PFTE and FEP,

plasticizers were also found to be present. The report also tested a newer Xylan that contained even more

compounds including butylated hydroxy toluene (BHT), a series of methylphenyl siloxanes (a type of

silicone rubber), and a series of n-alkanes with carbon numbers from 21 to 31. Minor compounds were

also found in the new Xylan that included ethyl acetate, benzene, acetic acid, p or m-xylene, o-xylene,

several phthalates, hexadecanoic and octadecanoic acids, and an alkyl amide. These minor chemical

compounds were used as binding agents and additives during the manufacturing process to create a

complex chemical structure. As a result, the potential for particle and outgassing contamination to

astromaterials increased the complexity of understanding point sources of contamination during organic

monitoring. In addition, the Xylan study recognized that polyamides in the gloveboxes could potentially

give a false biochemical signal, particularly for research involving amino acids and proteins. However,

only JSC curation internal memos documented this hypothesis and this interpretation of the data set was

not noted in the final Xylan reports.

In August 1990, JSC implemented a plan for removal of Xylan from all curation laboratories. In most

cases, Teflon replaced Xylan for lab jacks and glovebox doors. However, most stainless steel bolts and

screws remained with no alternative for the anti-galling coating. This made it difficult to work with

glovebox windows, bolt-top sample containers, and fasteners in curation labs. As a result, since 1990

many bolt-top sample containers in long-term storage have required the bolts be cut or drilled to open the

containers.

The Ruska Laboratory findings on Xylan prompted a series of inquiries into potential contamination by

that material. After Ian Wright’s team studied the Ruska laboratory findings, they believed that

compounds described by Wright et al. (1989) Nature publication bore a resemblance to constituents of

Xylan. Wright et al. (1992) published an article in Proceedings of Lunar and Planetary Science entitled

“Xylan: A Potential Contaminant for Lunar Samples and Antarctic Meteorites.” This article retracts some

of the claims from their 1989 publication about finding organic compounds from Mars and concludes that

Xylan contamination may have the potential to hinder past and future scientific investigations of organics.

The article highlights the Xylan contamination found in JSC curation laboratories and includes some of

the results from the Ruska Laboratory report on Xylan.

The timeline for the 1972 introduction of Xylan into curation laboratories to the 1990 removal is well

documented through many internal NASA memos and reports. To date, the Xylan contamination story is

the best example of JSC organic contamination found that has adversely affected the scientific analyses of

21

astromaterials. The study of these memos and timeline of events could potentially be used as lessons

learned for the development of future curation practices.

2.4 Organic Contamination Review Group 1997

The discovery of possible polycyclic aromatic hydrocarbons (PAHs) and other biomarkers identified in

the ALH84001 Martian meteorite in 1996 motivated the next organic study in JSC curation (McKay et al.

1996; Bada et al. 1998; Golden et al. 2001 and 2004). In 1997, NASA commissioned the Organic

Contamination Review Group to review potential organic contamination in the Antarctic Meteorite

laboratory. Jeffrey Bada, Director of the NASA Specialized Center of Research and Training (NSCORT)

in Exobiology at the Scripps Institution of Oceanography, University of California at San Diego was the

chair of the committee that reviewed the handling and cleaning procedures in the laboratory. The

committee was charged with evaluating four types of contamination: 1) contamination of organic

compounds that have a major role in biochemistry, such as amino acids; 2) contamination of organic

compounds that are common in the environment, such as PAHs; 3) contamination of viable

microorganisms, such as bacteria; and 4) contamination with macromolecular biomolecules, such as

deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). However, the final Bada report (Bada et al.

1997) does not directly address the four types of contamination with new data.

The highlighted findings from the Bada report do include several interesting observations and

recommendations. The report first draws attention to a 1992 NASA memo written by John James who

was the JSC Chief Scientist for Toxicology at the time. The memo states that the potential for

contamination of samples can be linked to the use of nylon sample bags. This internal memo perhaps is a

continuation of further examining the polyamides contamination from Xylan, knowing that nylon bags

also contain polyamides. Heat sealing nylon and polyethylene bags generate many compounds.

Caprolactam, found on many Balazs test reports, is usually generated from pyrolysis of nylon-6 and can

hydrolyze to the non-protein amino acid 6-amino-n-hexanoic acid. In addition, heating polyethylene can

also liberate phthalates that are used as plasticizers.

The common use of nylon and polyethylene bags in JSC curation was first initiated in 1979 by LAPST in

view of the relatively high permeability of Teflon to water during cleaning at WSTF and JSC. Before

1979, the lunar and meteorite collection only used Teflon bags for samples. Budget cuts also prompted

JSC curation to find costs savings plans through reviews of curation procedures. An April 1, 1980, memo

written by James Townsend entitled “Cost Reduction in Cleaning” initiated several major changes to

curation: 1) the use of Teflon was changed to the use of nylon and polyethylene bags that was noted to

save $7972.00 (in 1980 dollars); 2) the use of pressurized IPA (85 psig) replaced the Toluene/Methanol

washing in many cleaning procedures (it should be noted that while this memo is written with

“Toluene/Methanol” washing; JSC-03243 cleaning procedures from this era only mentions a “3:1

Benzene/Methanol” washing and this may have been a clerical error); 3) the use of a black light

inspection, quality assurance procedures and the use of class 100 flow bench during final flush rinsing

was eliminated to save procedural time and personnel costs.

Below are condensed steps of the glovebox/cabinet nominal cleaning procedure entitled “Lunar Sample

Curatorial Facility Cleaning Procedures for Contamination Control” – JSC document #03243, June 1,

1981, which superseded the October 1, 1971, procedure version (appendix II has CP-1 pages 4 – 7):

22

Acid Wash 2% nitric acid solution with distilled water (when required)

1% Oakite Liqui-Det detergent solution with distilled water

Mechanical scrubbing with nylon brushes, scouring pads, Scotch Brite pads and stainless

steel toothbrushes

Rinse with distilled water

Isopropyl alcohol (IPA) rinse and gaseous nitrogen (GN2) dry

Black light inspection

1% Oakite Liqui-Det solution with distilled water (Millipore can at 85 psig)

Isopropyl alcohol (IPA) rinse (Millipore can at 85 psig)

Vacuum flask for liquid pickup and squeegee with GN2 dry

Acid Wash 2% nitric acid solution with distilled water (when required)

Freon 113 (Millipore can at 85 psig)

Perform particle counts, total hydrocarbon counts (THCs), and non-volatile residue (NVR)

analysis.

A separate degreasing procedure for cabinets in the 1981 procedure uses high-pressurized Freon 113 and

2% nitric acid wash along with mechanical scrubbing. The major difference between the 1971 JSC 03243

cleaning procedure is the replacement of the 3:1 Benzene/Methanol washing with IPA. Historically, the 3:1

benzene/methanol solution was used in the 1969 LRL high vacuum complex cleaning procedure for

degreasing. The addition of nitric acid in the procedure was initiated for concerns of lead contamination and

was not meant to be used for passivation of the stainless steel in the gloveboxes. After these cleaning

procedures were adopted on October 1, 1971 (JSC 03243), JSC curation entered a period that included

adapted cleaning procedures due to cost saving plans, chemical phase-outs, and safety issues without

officially investigating how this change will affect the laboratory cleanliness standards. Even though there

is little documentation for the reasons of these changes, the JSC 03243 cleaning procedure document can be

used as a primary source for lessons learned on cleaning protocols for over 40 years.

In the Bada final report, the committee also mentioned the lack of documentation when changes were

made in the JSC curation cleaning procedures. Specifically, the committee noted that curation tool

cleaning procedures were significantly changed by switching from Freon 113 to Ultra-pure Water (UPW)

in 1994. The committee states that the new cleaning procedure using UPW needs to be further

investigated to confirm that these changes do not hinder cleanliness standards. This change in the

cleaning procedures meant that tools and gloveboxes were no longer being adequately degreased by a

solvent and reducing organic contamination. The Organic Contamination Review Group also stated that

the cleaning procedures do not include organic contamination specifications and no data currently existed

in 1997 on organic contamination. In addition, the Bada report mentions that Isopods, containers used to

transport meteorites from Antarctica, could possibly be a “huge potential source of bioorganic

concentration” as well as flow benches used in the Meteorite laboratory that are continuously exposed to

humans and other biocontaminants. The Bada report provides two final recommendations: (1) JSC

curation must establish routine organic testing of the Meteorite lab and UPW with TOC analysis; and (2)

JSC curation must have more control of samples and segregation of unique meteorite samples. While the

Meteorite lab today does not routinely measure for organics, the UPW is monitored by TOC and unique

samples are segregated in the Meteorite laboratory.

23

JSC curation began other studies in organic contamination from 1998 to 2001 in addition to those

surrounding ALH84001. Both the Genesis solar wind mission and a potential, future Mars Sample

Return mission prompted several small studies on organics contamination in curation. JSC Center

Director Discretionary Funding was used to conduct several organic baseline tests in Lunar and Meteorite

laboratories. These studies were conducted serendipitously at the same time that the Tagish Lake

meteorite was examined at JSC in 2000. However, no results were published related to Tagish Lake or

ALH84001 involving these organic tests. In addition to organic testing, several biological investigations

on extremophiles were conducted in the JSC Genesis laboratory and compared with other NASA

cleanroom environments (Venkateswaran et al. 2004; La Duc et al. 2007; Moissl et al. 2007, 2008;

Moissl-Eichinger 2011).

2.5 Glovebox Organic Contamination Results 1998 to Present

For Lunar and Meteorite curation laboratory gloveboxes, no documents are known to exist before 1998

concerning organic analyses. This report has compiled all existing documents from organic tests that

have been completed by JSC curation since 1998. The following analyses are for all glovebox testing

prior to the 2012 organic baseline study. In addition, some of the glovebox testing was in conjunction

with cleanroom testing. In all of these cases, we have provided all organic testing data that include both

gloveboxes and cleanrooms for comparison.

2.5.1 1998 Meteorite Laboratory Organic Analyses

The first in-air organics sampling was taken in 1998 in the Meteorite laboratory. The testing included the

laboratory cleanroom and inside the Mars meteorite glovebox. Organics were collected with an adsorbent

inside a stainless steel tube connected to a pump. The procedure is explained in more detail in the 2012

organic in air analysis in the next section. The adsorbent tube was analyzed at Balazs Analytics, Inc. by

thermal desorption gas chromatography mass spectroscopy (TD-GC-MS) and the results were given in

nanograms per liter (ng/L). The asterisks in all of the Balazs reports indicate that while a compound may

have been detected, it was below the reporting limit of the instrumentation. For example, in the 1998

Study of Organics in Air, Trichloroethylene (TCE) has an asterisk. This means that the instrument

identified a peak for TCE, however, the concentration of TCE was below 1.0 ng/L.

24

Figure 8: 1998 Balazs Report.

The 1998 Meteorite laboratory results show that the cleanroom has almost six times the amount of

hydrocarbons present in the glovebox. While it is typical that more hydrocarbons are present inside the

cleanroom than in a GN2 glovebox environment, these numbers are relatively high. The hydrocarbons

probably arise from offgassing plastics and heat sealing. The 1998 Balazs report suggests that aromatic

compounds such as toluene, ethylbenzene, xylenes and alkybenzenes and aliphatic compounds such as

low- to medium-boil hydrocarbons are common urban air pollutants from gasoline and diesel and may

also be used as solvents. Fluorocarbons and certain plasticizers are also present in these samples and

many of these organic compounds are most likely from sample bags and handling supplies. The report

suggests that the fluorocarbons detected in the Meteorite laboratory, room center, may be from

refrigerants. Caprolactam was detected at very low levels only in the Mars cabinet outlet. Caprolactam is

used in the manufacturing of nylon-6 and as a solvent for high molecular weight polymers. Therefore, the

practice of heat sealing nylon bags will outgas caprolactam. Isopropanol, butanol, propoxypropanol, 2-

butoxyethanol, butoxypropanol, dipropyleneglycol, and methoxyproxypropanol may be solvents. High

Hydrocarbons

Control

Blank

(ng/L)

Meteorite

Cleanroom

TD-GC-MS

Results

(ng/L)

Mars

Glovebox

TD-GC-MS

Results

(ng/L)

Low boilers C6-C10 10 63 16

Medium boilers >C10-C20 2 93 11

High boilers >C20 * 1 *

Sum >= C6 12 157 27

Identified Organic Compounds

Benezene * 1 *

Trichloroethylene * * *

Toluene 2 4 3

Tetrachlorethylene * * *

Ethylbenzene * 1 *

m, p-Xylenes * 1 *

Styrene * * *

o-Xylene * 1 *

NMP <0.5 <0.5 <0.5

Hexamethyldisiloxane <0.1 <0.1 <0.1

Cyclo(Me2SiO)3 <0.1 2.9 5.8

Cyclo(Me2SiO)4 <0.1 2.6 3

Cyclo(Me2SiO)5 <0.1 26 1

TXIB <0.1 0.8 <0.1

Fluorocarbons * 6 *

Isopropanol * 1 2

C6-C10 Hydrocarbons 8 32 10

Butanol + benzene * 1 *

Propoxypropanol * 3 *

2-Butoxypropanol 2 *

Butoxypropanol * 6 *

C11-C18 Hydrocarbons 1 43 3

C3-benzene+dipropylene glycol * 6 *

Methoxypropoxypropanol * 1 *

2-Ethylhexanol * 3 0.3

Nonanal * 2 *

Caprolactam * * 0.2

Cyclo(Me2SiO)6 * 2 0.3

Cyclo(Me2SiO)7 * * 0.5

diethyl phthalate * 0.9 *

dibutyl phthalate * 0.4 *

dioctyl phthalate (DOP) * 0.1 *

1998 Study of Organics in Air

* Reporting Limit = < 1 ng/L

25

levels of silicones (cyclic siloxanes) were also detected in both samples. Silicone contaminants often

originate from silicone sealants used in adhesives, flooring, the seals on High-Efficiency Particulate Air

(HEPA) and Ultra-low Penetration Air (ULPA) filters, and cleanroom wall joints. Siloxanes are also used

as lubricants in motors, and elastomers in gaskets. JSC curation labs frequently use silicone tapes and the

meteorite processing lab contains two freezers with motors. The common plasticizers 2,2,4-trimethyl-1,3-

pentanediol diisobutyrate (TXIB), diethyl phthalate, dibutyl phthalate, and DOP were detected in the

Meteorite lab room center. 2-Ethylhexanol was detected in both samples and is a common impurity in

plasticizers and may form as a hydrolysis or decomposition product of dioctyl phthalate. The report

suggests that most of the compounds detected are commonly found in industrial indoor air.

Schilling and Schneider (1998) further interpreted the Balazs 1998 report for JSC curation. They suggest

that hydrocarbons, benzene, toluene and xylenes are common contaminates from outside Houston air

entering the laboratory through the air handling system. The report cites that Houston air routinely

contains levels of these chemicals on the order of 5 to 10 ng/L. The report further suggests that butanol is

from human metabolic by-products and fluorocarbons are most likely the result of residual Freon 113 that

was once used for cleaning and/or the use of freezers inside the lab. The isopropanol, butanol,

propoxypropanol, 2-butoxyethanol, butoxypropanol, dipropyleneglycol, and methoxyproxypropanol

found are thought to be from outgassing of flooring, paints, markers and wet wipes in the lab. Sample

bags, vinyl gloves, gasket materials and other room plastics were linked with TXIB, diethyl phthalate,

dibutyl phthalate, and DOP. Schilling and Schneider (1999) also reported finding bacteria colonies in the

meteorite processing laboratory on the order of 7.9 to 11.8 colony forming units per cubic meter

(CFU/m3) dependent on the growth media.

The overall 1998 organic levels from the Mars cabinet outlet were lower than in the Meteorite lab, room

center, which is to be expected. However, these results seem relatively high compared with all other

Balazs data in JSC curation. In general, organics in air testing will produce higher precision results for

understanding the volatile organic compounds compared to organic wafer testing. However, it should be

noted that no other data exist for direct comparison from 1998. The Balazs report does state that JSC

curation should conduct more tests with heat sealing nylon bags. Since the meteorite lab is the only lab

that has multiple freezers inside a cleanroom at JSC, further investigation may also be warranted with

respect to refrigerant offgassing and cleanliness of the cleanroom laboratory.

2.5.2 Dixon Report: Evaluation of Organic Contamination in Curation

In 2000, Eleanor Dixon wrote an internal unpublished report entitled “Storage and Processing of

Extraterrestrial Samples from the Standpoint of Nitrogen Gas Purity: a Progress Report” (Dixon 2000).

While the report focused on gaseous nitrogen (GN2) purity and contamination, the report provides a

detailed analysis of the Balazs wafer organic tests conducted in 2000. The Dixon study also provides the

first organic test conducted on the JSC curation 45 psi house GN2 main supply pipe located in mechanical

room 1108 of B31N. A May 18, 2000 Balazs test report provides the organic results from a TD-GC-MS

analysis of organics in air by proprietary adsorbent inside a stainless steel tube exposed to the GN2 for 24

hours with a 100 mL/min flow. The hydrocarbon boilers showed a value of 2.0 ng/L of C7 – C10 versus a

“shipping control” blank designed to monitor contaminants accrued during shipping which showed 0.9

ng/L with all others below the reporting limit of 0.2 ng/L. In addition, toluene was reported at 1.1 ng/L

(shipping control = 0.5 ng/L) and 4.3 ng/L of C7 hydrocarbon (shipping control = 1.1 ng/L). All other

detected compounds were below the 0.2 ng/L reporting limit. Since the control also contained C7

26

hydrocarbons and toluene above reporting limits, Dixon’s report suggests that the special grade C LN2

boil-off between the tank and main mechanical room in 2000 was relatively free of organics. Air Product,

Inc., the LN2 supplier in 2000, certifies that the special grade C LN2 delivered to JSC will contain < 0.1

ppm of hydrocarbons and states this will be mostly methane. As a comparison, subsequent GN2 testing

in B31 and B31N in 2004 and 2012, reported later in this report, detected no organics >C7 with a

reporting limit of < 0.1 ng/L.

In January 2000, silicon wafer organic tests were conducted in the Genesis, Meteorite and Lunar

laboratories simultaneously. These tests were conducted in the following locations: (1) Genesis ISO class

4 cleanroom where wafers were exposed in room center of room 1107 and 1112; (2) Lunar laboratory

glovebox, Apollo 16 cabinet 307-38 (PSL-38), where the pristine processing glovebox was cleaned and

not used before testing; (3) Lunar laboratory glovebox, returned sample cabinet 309-49 (RSL-49), where

the wafer samples were exposed to heat sealing sample bags. Ten heat-seals each of Teflon, nylon and

polyethylene bags were performed in RSL-49; and (4) Meteorite laboratory Mars meteorite glovebox

(MPL-Met Mars). All silicon wafers were exposed for 42 – 47 hours in each location and analyzed by

TD-GC-MS. The Balazs and Dixon reports do not mention that the RSL-49 or MPL-Met Mars

gloveboxes were cleaned before testing. Therefore, we assume that the PSL-38 lunar glovebox was the

only glovebox cleaned before the experiment. Figures 9 – 11 show images of the gloveboxes and figure

12 reports the results from testing.

Figure 9: Lunar Lab Glovebox Apollo 16 – Cabinet 307-38 (PSL-38).

Figure 10: Lunar Lab Glovebox – Cabinet 309-49 (RSL-49).

Figure 11: Mars Meteorite cabinet in the Meteorite Curation Laboratory.

27

Figure 12: January 2000 Balazs Report.

The results show that the RSL-49 has the most contaminants compared to the other two gloveboxes. A

comparison between all three gloveboxes provides an insight into the distribution of different

contaminants and sources as well as the impact from heat sealing Teflon, nylon, and polyethylene bags.

The PSL-38 organic concentrations could potentially show the lowest possible organic loads using the

2000 glovebox cabinet cleaning procedures. The results in both the PSL-38 and MPL-Met Mars

gloveboxes are slightly lower, but not much lower than RSL-49. Dixon interprets these results to mean

Hydrocarbons

Control

Blank

(ng/cm2)

Genesis 1112

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Genesis 1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Lunar

Glovebox

PSL-38

TD-GC-MS

Results

(ng/cm2)

Lunar

Glovebox

RSL-49**

TD-GC-

MS

Results

(ng/cm2)

Meteoroite

Glovebox

MPL-MET

MARS TD-

GC-MS

Results

(ng/cm2)

Low boilers C7-C10 0.3 0.97 0.57 0.53 0.64 0.74

Medium boilers >C10-C20 0.61 20.89 16.86 4.93 10.15 5.55

High boilers >C20 0.17 4.44 3.25 0.81 1.72 1.3

Sum >= C7 1.07 26.3 20.67 6.28 12.51 7.59

Identified Organic Compounds

NMP * * * * * *

Hexamethyldisiloxane * * * * * *

Cyclo(Me2SiO)3 * 0.08 * * * *

Cyclo(Me2SiO)4 * * * * * *

Cyclo(Me2SiO)5 * * * 0.09 * 0.09

TXIB * 3.5 3.08 0.13 0.18 0.24

Dibutylamine * * * 0.09 0.7 *

Caprolactam * 0.11 * 0.11 3.63 0.17

N, N-dibutylformamide * * * 1.59 1.13 0.57

Dimethylcyclohexanol * 0.17 0.2 * * *

Isopropenylbenzene * 0.29 0.39 * * *

N-N-dibutylacetamide * * * 0.22 0.35 0.08

Isopropenylacetophenone * 1.02 1.09 * * *

Alkyl ester * 0.42 0.2 * * *

Diacetylbenzene * 1.36 0.57 * * *

Unkown (me/: 43, 163) * 0.83 0.28 * * *

Cyclo(Me2SiO)7 * 0.11 0.08 0.07 * *

Diethyl phthalate (DEP) * * * * * 0.26

Cyclo(Me2SiO)8 * 0.89 0.73 0.29 0.67 *

Dodecanamide * 0.15 * * * *

Other siloxanes * 0.41 0.4 * * *

Didecyl ester of decanedioic acid * 0.08 0.12 * * *

Isopropyl myristate * 0.12 0.14 * * 0.08

Diisobutyl phthalate * 0.33 0.48 * * *

Cyclo(Me2SiO)9 * 1.17 1.3 0.08 0.25 *

Dibutyl phthalate (DBP) * 0.34 0.33 0.15 1.02 *

Cyclo(Me2SiO)10 * 0.28 0.26 * 0.08 *

* Reporting Limit = < 0.08 ng/cm2

January 2000 Organic Wafer Testing

** Note heat sealing in RSL-49 during testing

28

that the higher organic concentrations in RSL-49 are directly related to the release of organics due to heat

sealing of sample bags. In addition to organic additives from heat sealing, these results may also show

the difference between a clean and unclean glovebox since the cleaning dates are not documented. A

comparison of the results between RSL-49 and PSL-38 show that the RSL-49 glovebox environment has

higher concentrations of dibutyl phthalate (DBP), cyclo(Me2SiO)x, TXIB, N-N dibutylacetamide, and

caprolactam. The relatively high concentrations of these organics in glovebox RSL-49 suggests that

increase volatilization may have occurred during heat-sealing of sample bags. The concentrations of

medium and high boiling point hydrocarbons are much higher for all of the gloveboxes than for the

control wafer. Since high concentrations of organics are present in PSL-38, relative to the control wafer,

suggests that other sources of organic contamination exist in addition to the organics released from heat

sealing in RSL-49. The role of organic contaminant accumulation during different GN2 flow rates inside

gloveboxes is also not known. For example, in the Lunar laboratory, sample processors routinely adjust

the gloveboxes from a low flow rate of 10 standard cubic feet per hour (scfh) during static non-working

hours compared to 100 scfh during the time when they are working inside the glovebox. This was

adopted in the early 1980s to save on GN2 delivery costs. Dixon also mentions that oil in the mechanical

room can commonly contribute to organic contamination by permeating through the GN2 line

connections. However, Dixon states that it is very unlikely that the B31N GN2 supply to the curation

gloveboxes experienced significant contamination from the mechanical room.

The results also show that all of the gloveboxes are less contaminated by organics compared to the

Genesis cleanrooms 1107 and 1112. Higher levels of hydrocarbons are noticeable in the 2000 results.

There are elevated levels of TXIB, isopropenyl acetophenone, diacetylbenzene, and silicone complexes

(cyclo(Me2SiO)x). The gloveboxes and Genesis cleanroom both have relatively high amounts of amides

(for example caprolactam), as well as DBP and TXIB. Dixon also mentions that caprolactam

contamination is possible due to nylon bag usage, as well as contamination by TXIB and DBP plasticizer

additives. The silicones detected are possibly due to adhesives in the ULPA fan filter units and the newly

constructed cleanroom walls and flooring. Concentrations of organic compounds found in the Genesis

cleanroom and PSL-38 glovebox show that Genesis has much higher levels. The gloveboxes seem to

have additional compounds that are not found in the Genesis cleanroom, such as N-N dibutylformamide,

N-N dibutylacetamide, dibutylamine and cyclo(Me2SiO)5. Similarly, siloxanes are found much more in

the Genesis cleanroom compared to the gloveboxes. Dixon also mentioned that it is difficult to determine

whether the organic compounds only found in the gloveboxes (and not from heat sealing) are from

organic materials used in the gloveboxes or from the introduction of GN2 organic contamination.

However, it is noteworthy that the highest amount of N-N dibutylformamide is found in PSL-38, which

has six neoprene gloves as opposed to four neoprene gloves in both the RSL-49 and MPL-Met Mars

gloveboxes.

The April 2000, Balazs organic testing was conducted for the meteorite carbonaceous chondrite glovebox

and the Genesis Terra Universal nitrogen storage cabinet. The Genesis cabinet was connected to a Terra

Universal Nitroplex nitrogen purge system that contained many unknown rubber gaskets and plastics that

were purported to have offgassed into the stainless steel cabinet. Due to results of this test, the Nitroplex

system was removed. As a result, the meteorite glovebox was found to be much more organically clean

compared to similar testing performed in January 2000. The carbonaceous chondrite glovebox does show

detectable hydrocarbons, TXIB, DMF, and diethyl phthalate (DEP). TXIB is mainly a plasticizer and can

be found in the manufacturing of vinyl flooring, walls covering, automotive plastics, nail care, and in

many poly vinyl chloride (PVC) and rubber manufacturing. DEP is a plasticizer largely used in the

fragrance industry as well as the processing of cellulose acetates. DMF is a solvent used in production of

29

acrylic fibers and plastics. In addition, DMF can be found in the manufacturing of pesticides, adhesives,

films, and surface coatings. The Genesis cabinet had high levels of hydrocarbons, TXIB, and cyclic

tetramethylene adipate. These are common plasticizers added to floor tiles, plastic curtains, and coatings.

However, these elevated plasticizers could possibly be due to the Nitroplex system.

Figure 13: April 2000 Balazs Report.

Hydrocarbons

Genesis

Cabinet

Control

Blank

(ng/cm2)

Genesis

Cabinet

TD-GC-MS

Results

(ng/cm2)

Meteorite

Glovebox

Control

Blank

(ng/cm2)

Meteorite

Glovebox

TD-GC-MS

Results

(ng/cm2)

Low boilers C7-C10 0.3 0.7 0.1 0.1

Medium boilers >C10-C20 1.6 16.2 0.2 0.2

High boilers >C20 0.1 0.9 0.1 0.5

Sum >= C7 2 17.8 0.4 0.8

Identified Organic Compounds

NMP * * * *

Hexamethyldisiloxane * * * *

Cyclo(Me2SiO)3 * * * *

Cyclo(Me2SiO)4 * * * *

Cyclo(Me2SiO)5 * * * *

TXIB 0.1 1 * 0.2

Diacetoxy butane * 0.2 * *

Butoxyethoxy ethanol * 0.2 * *

Caprolactam * 0.1 * *

N, N-dimethyl formamide * * * 0.1

Unknown (m/z: 55, 84, 112, 142) * 0.3 * *

Isopropenyl acetophenone 0.2 0.2 * *

Unknown (m/z: 43, 56, 71, 173) * 0.4 * *

Diacetyl benzene 0.2 0.4 * *

Cyclic tetramethylene adipate * 5.4 * *

Adipic acid derivative * 0.2 * *

Diethyl phthalate (DEP) * * * 0.2

Unknown (m/z: 43, 57, 101, 127) * 1.9 * *

Unknown (m/z: 43, 55, 115, 127) * 0.9 * *

Unknown (m/z: 43, 55, 127, 155, 183) * 0.6 * *

Dibutyl phthalate (DBP) * 0.1 * *

Unknown (m/z: 43, 55, 127, 155, 183) * 0.3 * *

Unknown (m/z: 57, 165, 267, 282) * * * 0.1

April 2000 Organic Wafer Testing

* Reporting Limit = < 0.1 ng/cm2

30

2.5.3 White Sands Test Facility Glovebox Glove Analyses In 2001, samples of potential glovebox glove materials were sent to the NASA WSTF for organic offgas

testing by NASA-STD-6001c; Test 7: Determination of Offgassed Products. The intent of this test was to

determine the glove material that generated the least organic contamination. The glove offgassing results

show many different hydrocarbons, plasticizers, and rubber chemicals. Butyl rubber has the lowest

amount of organic species overall with carbon monoxide as the most voluminous constituent. For Viton

B, C10 – C13 hydrocarbons, CO, and methylisobutylketone contribute the predominant offgassing

chemicals. Neoprene shows a strong offgassing of carbonyl sulfide, CO, acetone, and C10 – C12

hydrocarbons. Hypalon gloves generate carbonyl sulfide, sulfur dioxide, C10 – C12 hydrocarbons, and

xylenes. IPA is found to be a relatively common contaminant for all glove materials, especially in the

Viton B and Hypalon results. However, IPA is commonly used during glove cleaning, which is the most

likely source for the IPA.

Figure 14: 2001 WSTF outgassing test results from glovebox gloves.

Identified Compounds

Neoprene GW

(ppm)

Viton B

(ppm)

Chlorobutyl

Exxon 268

(ppm)

Hypalon

(ppm)

2·Nitropropane 40 * * *

Acetaldehyde 140 30 * 10

Acetone 270 100 5 10

Acrolein * * * 5

Acetonitrile 7 * * *

Butene 200 * 20 *

Butyraldehyde 170 * * *

C7 Ketone * * * 6

C7 Saturated aliphatic hydrocarbons * * 5 *

C8 – C9 Saturated aliphatic hydrocarbons * 40 * *

C8 – C9 Saturated and unsaturated aliphatic hydrocarbons * * * 20

C9 Aromatic hydrocarbon * * * 5

C10 – C11 Saturated aliphatic hydrocarbons * * 40 *

C10 – C12 Saturated aliphatic hydrocarbons 230 * * 280

C10 – C13 Saturated aliphatic hydrocarbons * 410 * *

C14 Saturated aliphatic hydrocarbons 50 * * *

Carbon disulfide 30 * * *

Carbon monoxide 670 280 300 100

Carbonyl sulfide 4400 * 30 500

Decamethylcyclopentasiloxane * * * 6

Difluorodimethyl silane * * 30 *

Ethyl benzene 5 5 10 20

Hexamethylcyclotrisiloxane 5 20 * *

Isobutyraldehyde * 50 * *

Isopropyl alcohol 200 15000 5 1200

Methylethylketone 9 * * *

Methylisobutylketone * 200 * 7

Methyl isopropyl ether * * 6 *

Octamethylcyclotetrasiloxane * * * 30

Sulfur dioxide * * * 490

Toluene 7 5 5 7

Xylenes 30 5 50 180

Unidentified component * * 5 *

* Below reporting limit

Glovebox Gloves WSTF Outgassing Test 2001

31

The glove material results are reported in a 2001 unpublished Worcester Polytechnic Institute BA theses

by Eric Kenney and Michael Young entitled “Glove Material Selection for Cleanroom Gloveboxes”

(Kenney and Young 2001). This glovebox glove report suggested that Hypalon and Viton shed many

fewer particles than butyl rubber and neoprene. Butyl rubber is the least permeable material followed by

Hypalon, Viton, and neoprene. Butyl rubber was the least clean material and generated the most particles

during cleaning. Viton was the cleanest material and had the lowest TOC counts. However, Viton was

observed to be tacky after cleaning.

This study recommended the replacement of neoprene with chlorosulfonated polyethylene (Hypalon)

gloves manufactured by North Safety based on criteria for offgassing, permeability, particle shedding, and

cleanability. Since this study, North Safety now manufactures a Hypalon/neoprene glove that combines

the dexterity and flexibility of neoprene and the chemical resistance of Hypalon. Honeywell also

manufactures a polyurethane/chlorosulfonated polyethylene glove, which is Hypalon on the outside and

polyurethane on the inside that lowers the permeability and allows easy removal of the hand/arm. Species

of offgassing or shed particles may be an important criterion depending on analytical goals; e.g. sulfur or

chlorine isotopes. It is also important to mention that many of the common plasticizers, solvents, and

silicone complexes can also be found in beauty products such as perfumes, hand creams, and nail polish.

Therefore, the possibility exists that contamination by these species is from human use of gloveboxes

where organics migrate through the neoprene gloves, the same glove material that is predominately used

in the Meteorite and Lunar laboratories.

2.5.4 Contamination by Glovebox Materials: A Case Study

In 2007, an MBraun, Inc. glovebox was purchased for conducting preliminary cold curation experiments

(figure 15). The glovebox was constructed from 304 stainless steel brushed finished, expandable PTFE

Gore-Tex seals, Hypalon gloves, and polycarbonate window. The glovebox was also fitted with a -35°C

cold plate and freezer for sample storage. In 2012, the MBraun glovebox was modified for storage of

asteroidal samples collected by the Hayabusa JAXA mission, and placed inside an ISO class 5 cleanroom

in B31N, room 1106. The MBraun glovebox’s polycarbonate window was replaced with safety glass and

PTFE gaskets were replaced with Viton. The freezer and cold plate were also removed along with the

unknown plastic materials used in the antechamber door. The following Balazs organic results were

taken when the glovebox was used as a cold curation glovebox in 2008 and recent organic tests in 2012

for the modified Hayabusa glovebox. Since this is the same glovebox using different materials, this is an

excellent record of material changes for a modified glovebox. In addition, the MBraun glovebox used for

cold curation is the only data point for the use of an integrated cold trap for collecting organics. These

results can be viewed for the silicon wafer testing of the cold plate in 2008 (figure 16).

32

Figure 15: 2008 MBraun glovebox in B31N, Room

1106. Figure 16: 2008 Balazs organic wafer testing on

cold plate and weighing balance.

Figure 17: 2008 Balazs results for the MBraun glovebox organic testing.

Cold Curation

Hydrocarbons

Control

Blank

(ng/cm2)

Mbraun

Glovebox

Cold Plate

TD-GC-MS

Results

(ng/cm2)

Mbraun

Glovebox

TD-GC-MS

Results

(ng/cm2)

Low boilers C7-C10 * 0.2 0.1

Medium boilers >C10-C20 * 8.2 1.2

High boilers >C20 * 2.7 0.9

Sum >= C7 * 11.1 2.2

Identified Organic Compounds

Butanol * * *

Dimethyl benzyl amine * 1.7 *

Triethyl phosphate * 0.2 *

Caprolactam * 0.3 *

2,6-di-tert * * *

butylbenzoquinone * * *

Butyl hydroxy toluene (BHT) * * *

Unknown(m/z: 41, 55, 84,100, 129) * * *

TXIB + Diethyl phthalate * 0.2 *

Cyclododecane * 0.2 0.1

Unknown (m/z: 70, 77, 105,112, 123) * 0.3 *

Isoprpoyl myristate * * *

Diisobutyl phthalate * 0.2 *

Dibutyl phthalate * 0.2 *

Octasulfur * 0.2 *

C6-C9 Hydrocarbons * * *

C16-C20 Hydrocarbon * 3.4 0.5

Possible fluorochlorocarbons (m/z: 85, 101, 135,151) * 0.8 0.4

* Reporting Limit = < 0.1 ng/cm2

2008 Testing

33

The 2008 glovebox configuration consisted of PTFE Gore-Tex seals, Hypalon gloves, and Lexan

(polycarbonate) window. The results in figure 17 show three organics in both wafers: hydrocarbons,

cyclododecane, and possible fluorochlorocarbons. Cyclododecane is used as an intermediate in the

production of flame retardants, detergents and other chemicals. Fluorochlorocarbons are generally

associated with Freon type products. Given the amount of unknown material in the MBraun glovebox, it is

difficult to pinpoint the nature of this contamination. However, we can speculate that the cold plate, freezer,

antechamber door handles, and viewing window are the most obvious source. As expected, the organic

contamination load is much higher on the cold plate, acting as a contamination cold trap. This is noticeable

from the hydrocarbons concentrations. In addition, dimethyl benzylamine and C16 – C20 hydrocarbons are

relatively high. Dimethyl benzylamine is found in polyurethane products and epoxy resins.

Figure 18: 2012 Balazs report for the MBraun glovebox organic testing for the Hayabusa Laboratory.

Hayabusa Laboratory

Hydrocarbons

Control

Blank

(ng/cm2)

Hayabusa

MBraun

Glovebox TD-

GC-MS Results

(ng/cm2)

Hayabusa

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Low boilers C7-C10 * 0.2 0.6

Medium boilers >C10-C20 * 0.8 8.9

High boilers >C20 * 0.1 0.2

Sum >= C7 * 1.1 9.7

Identified Organic Compounds

MIBK * * *

Butoxy ethanol * * *

Benzaldehyde * * *

Dipropylene glycol methyl ether * * *

2-Propanol, 1-(2-methoxypropoxy)- * * *

Ethyl hexanol * * *

Acetophenone * * *

Ethanol, 2-(2-butoxyethoxy)- + Cyclo(Me2SiO)5 * * 0.2

Caprolactam * 0.1 0.7

Alkyl ester * * 0.5

Texanol * * 0.8

p-Diacetylbenzene * * 0.1

Diisopropyl adipate * * *

Diisopropyl phenol * * 0.1

2,6-di-tert-Butylquinone * * *

2,6-di(t-butyl)-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one * * *

BHT-quinone-methide + Ethanone, 1-[4-(1-hydroxy-1-methylethyl)phenyl]- * * *

Cyclic tetramehtylene adipate * * *

Diethyl phthalate * * 0.4

TXIB * * 0.8

Hexadecamethylheptasiloxane * * *

Cyclooctasiloxane, hexadecamethyl- * * 0.3

BHT-aldehyde * * 0.2

3,5-di-tert-Butyl-4-hydroxybenzaldehyde * * *

Isopropyl Myristate * * *

Diisobutyl phthalate * * 0.2

Cyclo(Me2SiO)9 * * 0.2

Dibutyl phthalate * * 0.1

Cyclo(Me2SiO)10 * * *

Cyclo(Me2SiO)11 * * *

Hexanedioic acid, bis(2-ethylhexyl) ester * * *

Di-n-octyl phthalate * * *

Siloxane * * 0.1

* Reporting Limit = < 0.1 ng/cm2

July 2012 Organic Wafer Testing

34

The 2012 Hayabusa MBraun glovebox configuration consisted of Viton seals, Hypalon gloves, and glass

window. The results in figure 18 show a very low level of organics, mostly below the reporting limit of <

0.1 ng/cm2. The only organic compounds detected are a small amount of hydrocarbons and caprolactam.

This contamination may have been a result of testing while simultaneously inserting a polypropylene box

holding a sampling wafer for inorganic particulate contamination testing. The box was previously stored

in a nylon bag and may have absorbed caprolactam during transport. It should also be noted that we do

not find certain organics in the MBraun glovebox compared with the Lunar and Meteorite laboratory

gloveboxes. With the clear absence of detectable organics such as TXIB, DMF, and DEP, N-N

dibutylformamide, N-N dibutylacetamide, and dibutylamine, we can speculate that this may have been

caused by changing the gloves from neoprene to Hypalon and/or changing the polycarbonate window to

glass. Polycarbonate windows have a large surface area and may potentially offgas more than gloves

interacting with the GN2 environment. The Hayabusa room 1106 cleanroom results show a similar

pattern with the Genesis cleanroom with the presence of plasticizers and silicone adhesives. However,

Texanol was detected and is one of the main chemicals in latex paint as well as some adhesives. In

addition, detectable levels of TXIB, a plasticizer, can also be found in paints and adhesives. The

cleanroom results also show that caprolactam was detected and possibly due to the extensive use of nylon

bags in the laboratory.

2.6 Cleanroom Organic Contamination Results 2000 to Present The use of reduced particulate cleanrooms for handling astromaterials can be traced to the Apollo

program. The LRL in JSC B37 was the first curation facility to be concerned about monitoring and

lowering air particulate contamination. In addition, LRL tool cleaning procedures required the use of ISO

class 5 (former class 100) laminar air flow during final cleaning steps. The LRL also began conducting

particulate testing and monitoring inside the SNAP and NNPL lines during Apollo 14 and later missions

(Reynolds et al. 1972). However, gloveboxes inside the LRL were not required to utilize a certified

particulate reduced air flow. Instead, the B37 facility used a traditional filtered air handling systems to

clean laboratory air. The later-established lunar and meteorite curation laboratories also used gloveboxes

using air filtered through the building air handling system. In 1981, the cosmic dust laboratory

established a trend toward the use of more modern airflow filtration. Instead of using gloveboxes for

sample containment, sample processing of cosmic dust was conducted using ISO Class 5 laminar flow

workstations. The processing of samples under laminar flow proved to be cleaner with respect to

particulates than sample processing within a glovebox environment.

In 1998, the Genesis laboratory was established with two ISO class 4 cleanrooms and was considered to

be the first cleanroom in JSC curation to be modeled after semiconductor industry cleanrooms. The

Genesis lab was constructed on the first floor of B31N in the old lunar public viewing area. The

construction was state-of-the-art at the time with ULPA filtration fan filter units (FFUs) in the ceiling and

a raised floor to create a total laminar flow cleanroom environment. This room was sufficiently clean to

accommodate both preflight assembly of the science canister and post-flight sample processing. This

design allows the laminar air to flow directly from the FFU in the ceiling through the perforated floor and

back up the outside of the inner wall panel for recirculation to the FFU. The Stardust curation facility was

constructed in 2006 and Hayabusa in 2012. Both are ISO class 5 cleanrooms and also have laminar air

flow with ULPA FFU in the ceiling, but do not have a raised floor. This creates some turbulent air flow

at the bottom of the floor with the air exiting through the bottom wall panels. While Stardust and

35

Hayabusa laboratories do not have a raised floor, organic testing conducted in these cleanrooms should

give similar results to Genesis due to the similarities in cleanroom construction materials.

2.6.1 Genesis Laboratory Organic Analyses

The Genesis laboratory is the only curation laboratory that regularly tests for organic contamination. These

routine organic tests from 2000 to 2011 in both ISO 4 class cleanrooms 1112 and 1107 provide an excellent

baseline for organics in the JSC curation cleanrooms that are modeled after the semiconductor industry. In

2000, Balazs Analytical Inc. was contracted to provide all molecular organic testing by exposure of 6- or 8-

inch silicon wafer for 24 hours and measurement by TD-GC-MS. Early testing was documented in a 2001

Worcester Polytechnic Institute BA thesis by Dan Erickson and Kathy Pacheco entitled “Organic

Outgassing in NASA’s JSC Genesis Cleanrooms” (Erickson and Pacheco 2001). In addition, adsorbent

tube organic testing measured by TD-GC-MS analysis was conducted in 2001 and 2002 in the Genesis

cleanroom and on the Genesis GN2 in 2004. All Balazs reports were reviewed by the Genesis curator and

subsequently provided to the CAPTEM Genesis oversight subcommittee for review. The following are all

the organic results from the Genesis cleanroom from 2000 to 2011 (figures 19 to 23).

36

Figure 19: Balazs wafer exposure TD-GC-MS results for Genesis Laboratory from 2000 to 2001.

Genesis Cleanroom

Hydrocarbons

Genesis

Cleanroom

1107

Control

Blank

(ng/cm2)

Genesis

Cleanroom

1107

TD-GC-MS

Results

(ng/cm2)

Genesis

Cleanroom

1107

Control

Blank

(ng/cm2)

Genesis

Cleanroom

1107

TD-GC-MS

Results

(ng/cm2)

Genesis

Cleanroom

1112

Control

Blank

(ng/cm2)

Genesis

Cleanroom

1112

TD-GC-MS

Results

(ng/cm2)

Low boilers C7-C10 0.2 0.6 0.88 0.94 0.2 0.5

Medium boilers >C10-C20 0.3 17.9 0.37 15.35 0.3 6.4

High boilers >C20 * 2 0.43 3.57 * 3

Sum >= C7 0.5 20.5 1.68 19.86 0.5 9.9

Identified Organic Compounds

2-(2-Butoxyethoxy) ethanol 0.2

2-Octyl-3-isothiazolinone * 0.3 * 0.2 * *

4'-(hydroxymethlethyl)-acetophenone * * * * * 0.5

Acetophenone derivative * 1.8 * * * *

Alkyl ester * * * * * 0.1

Alkylphenol * * * 1.5 * *

Butoxyethoxy ethanol * 0.6 * 0.4 * *

C20 Hydrocarbon * * * * * *

Caprolactam * * * 0.1 * *

Cyclo(Me2SiO)10 * * * 0.2 * *

Cyclo(Me2SiO)11 * * * * * *

Cyclo(Me2SiO)3 * * * * * *

Cyclo(Me2SiO)4 * * * * * *

Cyclo(Me2SiO)5 * * * * 0.2 *

Cyclo(Me2SiO)8 * 0.2 * 0.2 * 0.1

Cyclo(Me2SiO)9 * * * * * 0.1

Dibutyl phthalate (DBP) * 0.4 * 0.3 * 0.1

Diethyl phthalate (DEP) * 0.3 * 0.8 * 0.1

Di-isobutyl phthalate * 0.8 * 0.7 * *

Di-isopropenylbenzene * * * * * 0.2

Dioctyl phthalate (DOP) * * * 0.2 * *

Dodecanamide * 0.1 * 0.1 * *

Hexamethyldisiloxane * * * * * *

Isopropyl myristate * 0.1 * 0.2 * 0.1

Naphthalene + Butoxethoxy ethanol + Cyclo (Me2SiO)5 * * * * * *

NMP * * * * * *

p-Acetyl acetophenone * 1.3 * * * 0.3

p-Acetyl-isopropenylbenzene * * * * * 0.5

Siloxane * * * 0.5 * *

Texanol * 0.4 * * * *

TXIB * 1.6 * 2.79 * 1

Unknown (m/z: 111, 125, 140) * * * * * *

Unknown (m/z: 115, 145, 160) * 1.1 * 0.7 * *

Unknown (m/z: 115, 158) * * * * * *

Unknown (m/z: 138, 208) * * * * * *

Unknown (m/z: 153, 183, 198) * * * * * *

Unknown (m/z: 43, 161, 176) * * * * * *

Unknown (m/z: 43, 163) * * * * * *

June 2000

* Reporting Limit = < 0.1 ng/cm2

August 2000 Feburary 2001

37

Figure 20: Balazs adsorbent tube TD-GC-MS results for Genesis Laboratory from 2001 and 2002.

Genesis Cleanroom

Hydrocarbons

Control

Blank

(ng/L)

Genesis 1112

Cleanroom

TD-GC-MS

Results (ng/L)

Control

Blank

(ng/L)

Genesis 1112

Cleanroom

TD-GC-MS

Results (ng/L)

Low boilers C7-C10 1.0 6.0 ** 12.0

Medium boilers >C10-C20 * 3.0 ** 8.0

High boilers >C20 * * ** **

Sum >= C7 1.0 9.0 ** 20.0

Identified Organic Compounds

Benzaldehyde * * ** **

Cyclo(Me2SiO)3 * * ** **

Cyclo(Me2SiO)4 * * ** **

Cyclo(Me2SiO)5 * * ** **

Ethyl hexanol * * ** **

Ethylbenzene * * ** **

Hexamethyldisiloxane * * ** **

m,p-Xylenes * * ** **

Methyl naphthalene isomers * * ** **

Naphthalene * * ** **

NMP * * ** **

o-Xylene * * ** **

Styrene * * ** **

Tetrachloroethylene * * ** **

Toluene * 2.0 ** **

TXIB * * ** **

November 2001 Testing September 2002 Testing

* Reporting Limit = < 1.0 ng/L

** Reporting Limit = < 2.0 ng/L

38

Figure 21: Balazs wafer exposure TD-GC-MS results for Genesis Laboratory from 2002 to 2004.

Genesis Cleanroom

Hydrocarbons

Control

Blank

(ng/cm2)

Genesis

1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Genesis

1112

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis

1112

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis 1107

Cleanroom TD-

GC-MS Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis

1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis

1112

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Low boilers C7-C10 0.1 1.1 0.9 * 0.7 0.1 0.7 0.1 1.1 0.2 0.7

Medium boilers >C10-C20 * 8.6 6.4 * 3.9 0.2 5.1 0.1 5.1 0.3 6.6

High boilers >C20 * 3.5 3 * 2.1 * 2.5 * 1.8 0.1 2

Sum >= C7 0.1 13.2 10.3 * 6.7 0.3 8.3 0.2 8.0 0.6 9.3

Identified Organic Compounds

2-(2-butoxy ethoxy) ethanol * 0.2 0.9 * * * 0.5 * * * 0.3

2-(2-Butoxyethoxy) ethanol + Cyclo (Me2SiO)7 * * * * 0.1 * * * * * *

2-n-Octyl-3 (2H)-lsothiazolone * * 0.1 * * * * * * * *

Acetyl phenyl propanol * * * * * * 0.2 * * * *

Alkyl acrylate * * * * * * * * * * *

Alkyl esters * 0.1 0.4 * 0.2 * 0.2 * 0.1 * 0.1

Alkyl nitrile * * * * * * 0.1 * * * *

Benzoic acid + 2-(2-butoxy ethoxy) ethanol * * * * * * * * 0.4 * *

Benzoic acid + Decanal * * * * * * * * * * 0.1

Butoxy ethanol * 0.1 * * * * * * * * *

C10 - C25 hydrocarbons * * * * 1.8 * * * * * *

C21-C25 Hydrocarbons * * * * * * * * * * 0.2

C21-C26 hydrocarbons * * * * * * 2.2 * 0.2 * *

C8 hydrocarbons * * * * * * 0.3 * 0.4 * 0.1

C8-C23 hydrocarbons * 0.2 0.4 * * * * * * * *

Caprolactam * 0.2 0.2 * 0.1 * 0.2 * 0.1 * 0.1

Cyclo (Me2SiO)10 * 0.1 * * * * * * * * *

Cyclo (Me2SiO)7 * * * * * * * * * * *

Cyclo (Me2SiO)8 * 0.1 0.1 * * * * * * * 0.1

Cyclo (Me2SiO)9 * 0.1 0.1 * * * * * * *

Cyclo(Me2SiO)6 * * * * * * * * * * 0.1

Cyclo(Me2SiO)7 + 2,6-di-tert-butyl benzoquinone * * * * * * * * * * 0.1

Diacetyl acetophenone * 0.5 0.5 * * * * * * * *

Diacetyl benzene * * * * * 0.3 * 0.3 * 0.4

Dibutyl phthalate * 0.1 0.2 * * * 0.1 * 0.1 * 0.1

Diethyl phthalate * 0.2 0.2 * 0.3 * 0.2 * 0.2 * 0.3

Diisobutyl phthalate * 0.1 0.6 * * * 0.4 * 0.2 * 0.1

Diisopropenyl benzene * 0.1 0.1 * 0.1 * * * 0.1 * 0.1

Diisopropyl phenol * 0.1 0.4 * 0.1 * * * 0.1 * 0.1

Dimethyl phthalate * * * * * * * * * * 0.1

Ethyl hexanal * * 0.1 * * * 0.1 * * * *

Hydroxymethylethyl-acetophenone * * * * 0.2 * * * * * *

Isopropenyl acetophenone * 0.6 0.5 * 0.2 * 0.3 * 0.4 * 0.6

Isopropyl myristate * * * * * * * * * * *

NMP * * * * * * * * * * 0.1

PGMEA * * * * * * * * * * *

Phenols * * * * * * * * * * *

Propylene glycol glyme isomers * * * * * * * * * * 0.1

Styrene * * * * * * * * * * *

TXIB * 0.4 0.4 * 0.3 * 0.4 * 0.3 * 0.4

Undecanonitrile * 0.1 0.1 * * * * * * * *

Unknown (m/z: 43, 55, 71, 95) * * * * * * * * * * *

Unknown (m/z: 55, 97, 150) * * * * 0.1 * * * * * *

Unknown (m/z: 55, 99, 173) * 0.1 0.1 * * * 0.1 * * * *

Unknown(m/z: 55, 84, 99, 173) * * * * * * * * * * 0.1

Unknown(m/z: 76,104,149,193) * * * * * * * * * * 0.1

June 2004 Testing

* Reporting Limit = < 0.1 ng/cm2

September 2002 Testing July 2003 Testing September 2003 Testing March 2004 Testing

39

Figure 22: Balazs wafer exposure TD-GC-MS results for Genesis Laboratory from 2005 to 2011.

The Genesis ISO 4 class cleanroom test results generally illustrate that hydrocarbons, plasticizers, and

silicone compounds are the primary organic contaminants in this environment. The Genesis 2000 and

2001 results show elevated levels of TXIB, p-Acetyl acetophenone, acetophenone derivatives, DEP, DBP,

diisobutyl phthalate (DIBP), and alkylphenol. The acetophenones are found mainly in fragrances and

Genesis Cleanroom

Hydrocarbons

Control

Blank

(ng/cm2)

Genesis

1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis

1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis 1107

Cleanroom TD-

GC-MS Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis

1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Control

Blank

(ng/cm2)

Genesis

1107

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Genesis

1112

Cleanroom

TD-GC-MS

Results

(ng/cm2)

Low boilers C7-C10 * 0.5 * 0.5 * 1.3 * 0.9 * 0.7 0.6

Medium boilers >C10-C20 * 8.2 * 7.3 * 6.1 * 11.8 * 9.2 10.4

High boilers >C20 * 2.7 * * * 1.9 * 2.8 * 4.4 2.8

Sum >= C7 * 11.4 * 7.8 * 9.3 * 15.5 * 14.3 13.8

Identified Organic Compounds

1-(2-Butoxyethoxy) ethanol * * * * * * * * * * *

2(2-Butoxyethoxy)ethanol + Cyclo(Me2SiO)5 * 0.2 * * * 0.2 * * * 0.2 0.2

2,6-di-butyl-2,5-cyclohexadiene-1,4-dione * * * * * * * * * * *

Acetyl acetophenone * 0.4 * 0.4 * * * * * * *

Alkyl ester * 0.3 * * * 0.3 * 3.2 * 0.4 0.6

Alkyl ester + Cyclo(Me2SiO)6 * * * * * 0.1 * * * * *

Alkyl nitrile * * * * * * * * * * *

Alkyl phthalate * * * * * * * * * * *

Butoxyethanol * * * * * * * * * * *

Butyl benzyl phthalate * * * * * * * * * 0.1 *

C12 hydrocarbon + Unknown(m/z:97,110) * * * * * * * * * 0.1 0.1

C18-C27 hydrocarbons * * * * * * * * * 0.2 0.2

C20-C24 hydrocarbons * * * * * * * 2.0 * * *

C5-C9 hydrocarbons * * * * * * * 0.6 * * *

C6-C7 hydrocarbons * * * * * * * * * 0.2 *

C6-C9 hydrocarbons * * * * * 0.4 * * * * *

C8 hydrocarbon * * * 0.4 * * * * * * *

C8-C25 Hydrocarbons * 0.6 * * * * * * * * *

Caprolactam * 0.1 * 0.3 * 0.3 * * * 0.1 0.1

Cyclo (Me2SiO)10 * * * * * * * * * * *

Cyclo (Me2SiO)4 * * * * * * * * * * *

Cyclo (Me2SiO)7 * 0.2 * * * * * 0.8 * * 0.1

Cyclo (Me2SiO)8 * 0.2 * * * 0.2 * 0.9 * * 0.4

Cyclo (Me2SiO)9 * 0.2 * * * * * * * 0.2 0.1

Cyclododecane * * * * * * * * * * *

Di(2-ethylhexyl)adipate * * * * * * * * * * *

Diacetyl benzene * * * * * 0.2 * * * * *

Dibutyl phthalate * 0.2 * 0.4 * 0.3 * 0.4 * 0.3 0.3

Didecyl sebacate * * * * * * * * * * *

Diethyl phthalate * 0.8 * 0.5 * 0.4 * 1.0 * 0.6 0.5

Diisobutyl phthalate * 0.4 * 0.5 * 0.3 * 0.6 * 0.5 0.3

Diisopropenylbenzene * * * * * * * * * * *

Diisopropyl adipate * * * * * * * * * * *

Diisopropyl phenol * 0.1 * * * * * * * * *

Dioctyl adipate * * * * * * * 0.2 * 0.1 *

Dioctyl phthalate * * * * * * * * * 1.0 0.2

Dipropyl phthalate * * * * * * * * * * *

Dipropyleneglycol * * * * * 0.1 * * * * *

Dodecanamide * * * * * * * * * 0.1 0.1

Dodecanenitrile * * * * * * * * * * *

Ethyl hexanol * 0.1 * * * 0.1 * 0.1 * * *

Hexadecamethylheptasiloxane * * * * * * * * * * *

Isopropenyl acetophenone + Cyclo(Me2SiO)6 * 0.2 * * * * * * * * *

Isopropyl myristate * * * * * * * * * * *

Methyl palmitate * * * * * * * * * * *

MIBK * * * * * * * * * * *

NMP * * * * * * * * * * *

Phenol * * * * * * * * * * *

Siloxane * * * * * * * 0.5 * * 0.1

Surfynol * * * * * * * * * * *

Texanol * * * * * * * * * 1.0 1.4

Triphenyl phosphate * * * * * * * * * * *

Tripropylene glycol * * * * * * * * * 0.5 0.6

TXIB * 0.8 * 0.9 * 0.3 * 0.9 * 0.5 0.5

Undecanenitrile * 0.1 * * * 0.1 * * * * *

Unknown (43, 71, 115, 145, 160) * * * * * * * * * * *

Unknown (m/z: 43, 163) * * * * * * * * * * *

Unknown (m/z: 55, 99, 173, 221 ) * 0.2 * * * * * * * * *

Unknown(m/z: 71 , 83, 101 , 113, 119) * * * * * 0.1 * * * * *

Unknown(m/z:43, 55, 71, 97, 110) * * * * * * * 0.2 * * *

Unknown(m/z:43,57,71,83,101,113,119,132, 147) * * * * * * * 0.2 * 0.5 0.2

Unknown(m/z:43,71,91,115,145,160) + Cyclo(Me2Sio)6 * * * * * * * * * * *

April 2010 Testing July 2011 Testing

* Reporting Limit = < 0.1 ng/cm2

May 2005 Testing May 2006 Testing October 2008 Testing

40

perfumes as well as resins used in inks and coatings. Alkylphenol is used in detergents and additives in

fuels, lubricants, polymers, high performance rubbers, phenolic resins, fragrances, thermoplastic

elastomers, fire retardants, oil field chemicals, and antioxidants. The TXIB, DEP, DBP, and DIBP are all

plasticizers. TXIB is widely used in the manufacturing of PVC, coatings for automotive plastics,

lithographic and letterpress oil-based inks, nail care products, phthalate-free diluents for methyl ethyl

ketone peroxide (MEKP) formulations, plastisols, sheet vinyl flooring, toys/sporting goods plastic

products, traffic cones, vinyl compounding and gloves, and common wall coverings. DEP is largely used

in the perfume and fragrance industry as well as the processing of cellulose acetates. The DBP plasticizer

is found in adhesives, solvents, and inks. DIBP is used in nitro cellulose plastic, nail polish, explosive

material, and lacquer manufacturing. These early Genesis results also show an increased use of isopropyl

compared with later years. This is most likely related to the use of IPA wipes and ultra-pure cleaning

solvents in the laboratory.

As a comparison with early years, the Genesis 2010-2011 results still show the increased levels of TXIB,

DEP, and DIBP plasticizers as well as DOP, used as a plasticizer in resins and elastomers. The test

results also show an increase in texanol and alkyl ester compared with earlier years. Texanol is most

commonly found in latex paint and ink coatings. The texanol and alkyl ester could also be derivatives in

plasticizers. All of these increased levels may be from renovations adjacent to the cleanrooms because in

2009 a new air handling system was installed in B31N, room 1108 adjacent to the Genesis laboratory. In

addition, the Genesis lab experienced a minor flood and underwent some renovations inside the

laboratory in 2010 before this testing. The texanol found in 2011 could also be from fresh wall painting

that was done outside room 1105 a few weeks before testing. The presence of silicone and plasticizers is

noticeably higher in the early years compared to the laboratory today. Silicone and plasticizers are

common in ULPA fan filter units, cleanroom paneling sealants, and flooring sealants. This is most likely

due to the change in offgassing of the new lab construction compared to the current lab that has had time

to offgas some products. It is also important to note that many of the common plasticizers, solvents, and

silicone complexes can also be found in beauty products such as perfumes, hand creams, and nail polish.

The Genesis laboratory has added cleanliness restrictions for personnel and the use of personnel hygiene

products has been very restrictive. However, we cannot rule out human contamination of the laboratory.

In addition, the air handling system brings in about 10% fresh outside air. Molecular organic

contamination < 0.1 to 0.2 µm from the local environment cannot be removed by filtration through ULPA

fan filter units (IEST-RP-CC001.5).

Figure 23 below is a summary plot for >C7 hydrocarbons in Genesis over time. The summary plot also

illustrates that the materials of the newly constructed cleanroom probably outgassed more in 2000

compared to other years. The other possible contributing factor for the increase in hydrocarbons could be

the assembly of the Genesis science canister with increased activity and personnel entering the lab.

Figure 23 also shows increased hydrocarbons between 2008 and 2010 – 2011. This could also be due to

the renovations in adjacent rooms around the time of the testing, such as the new air handler or flood

renovations. As a comparison to figure 23 wafer exposure results, figure 20 above shows the adsorbent

tube results in 2001 and 2002. The amount of >C7 hydrocarbons are almost doubled in 2002, but this may

be because adsorbent tubes usually provide a better indicator of volatile organic compounds (VOCs) than

exposed Si wafers. If adsorbents were used for testing in every year, we would probably see an increase

in >C7 hydrocarbons values.

41

Figure 23: Genesis Laboratory measured > C7 hydrocarbons from 2000 to 2011.

In 2004, the Genesis B31N house GN2 source was tested for organic contamination. The test consisted of

exposing a Balazs proprietary adsorbent tube to the GN2 supply in the Genesis mechanical room 1108

and Genesis cleanroom 1107. In addition, the GN2 supply was tested after passing through a Pall purifier

and particle filter in 1107 as well as the GN2 environment inside an array sample storage cabinet. The

adsorbent tubes were then analyzed by TD-GC-MS and the results are presented below in figure 24.

Figure 24: 2004 Balazs adsorbent tube TD-GC-MS results for GN2 in the Genesis Laboratory.

The 2004 GN2 organic tests shows that the GN2 house supply is free of organic contamination for >C7

hydrocarbons at < 0.1 ng/L. This also matches the results in 2013, shown later in this report. The GN2

supply after the Pall purifier/filter and inside the storage cabinet show increased low boiler hydrocarbons

at 0.4 ng/L. The TCE found in the cabinet could be from initial cleaning before installation inside the

0

5

10

15

20

25

30

20

00

20

01

20

02

20

03

20

04

20

05

20

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11

> C

7 H

ydro

carb

on

s (

ng

/cm

2)

Year

Genesis Laboratory > C7 Hydrocarbons

Genesis Room 1107

Genesis Room 1112

Genesis Cleanroom

Hydrocarbons

Control

Blank

(ng/L)

Genesis 1107

Array Cabinet

TD-GC-MS

Results

(ng/L)

Genesis 1107

GN2 After

Filter TD-GC-

MS Results

(ng/L)

Genesis 1107

GN2 Supply

TD-GC-MS

Results

(ng/L)

Mech Room

1108 GN2

Supply

TD-GC-MS

Results

(ng/L)

Low boilers C7-C10 * 0.4 0.4 * *

Medium boilers >C10-C20 * * * * *

High boilers >C20 * * * * *

Sum >= C7 * 0.4 0.4 * *

Identified Organic Compounds

Benzene * * 0.2 * *

C6 Hydrocarbons * * 3.8 * *

Ethyl benzene * * * * *

m,p-Xylene * * 0.1 * *

Trichloroethylene * 0.3 * * *

April 2004 Testing

* Reporting Limit = < 0.1 ng/L

42

laboratory. The increased hydrocarbons >C7, benzene, C6 hydrocarbons, and m,p-Xylene found are most

likely the result of Pall’s proprietary filter/purifier media.

2.6.2 Camenzind Report: Evaluation of Cleanroom Contamination

In 2000, Mark Camenzind, Senior Research Chemist of Balazs Analytical Laboratory was contracted by

NASA JSC curation to assess organic airborne contamination sources in all JSC curation cleanrooms and

evaluate alternative state-of-the-art concepts for the proposed future Mars Sample Handling Facility

(Camenzind 2000). Camenzind toured the JSC facility on August 31, 2000, to September 1, 2000. In

general, the report outlines laboratory processes for each lab and suggests alternative methods based on

the experience of the semiconductor industry. While the report discusses new methods for sampling

handling, including robotics for Mars sample handling, only the relevant findings will be highlighted

from Camenzind’s tour of the Lunar, Meteorite, and Genesis laboratories.

In the Lunar laboratory, Camenzind mentions that the heat sealing process causes outgassing of bag

materials similar to the Bada final report. The heat sealer works by heating a Nichrome wire with a

silicone strip backing surface, and welding the plastic by pressing it against this assembly. Unlike

silicone products that are made for high-temperature environments, the silicone heat sealer strip is

manufactured to slowly ablate over time and will readily outgas. Clean tools and samples that are heat

sealed in bags may have organic contamination by this process. As an alternative, Camenzind suggested

changing out the silicone strip for a better heat-tolerant material, such as Kalrez, Chemraz, or PEEK.

Camenzind also recommended that future missions should not use heat sealing. As an alternative, he

advocates bagged tools and samples should use zip-lock bags or “Gerry Tube” used in the food industry

for no-leak seals. The report also mentions the Lunar lab’s use of Polaroid film and two computers with

fans as potential sources of organic contamination.

In the Meteorite laboratory, two contamination sources were mentioned – the use of a polyester tape and

the Linoleum type flooring. Camenzind advises changing out the tape for a low-outgassing tape (Avery,

3M, etc.). The Linoleum floor was also recommended to be replaced with a more compatible cleanroom

flooring material. In addition, the report comments on the UPW system and the possible presence of

bacteria. During low water usage, biofilm growth can be of concern and bacteria may also be present in

the Reverse Osmosis (RO) system. Camenzind suggests that routine monitoring of the UPW system for

bacteria may be necessary.

In the Genesis laboratory, the Camenzind report listed several major sources for organic contamination:

Floor Tiles

ULPA filter potting compounds

ULPA filter gaskets

Tygon tubing

Desiccator door seals

Plastic Flow meters

Oven door seals and exhaust manifold

Floor pedestal rubber material

The report also outlines the Balazs 2000 Genesis cleanroom organic testing results related to these

materials. The large amount of plasticizers found, such as TXIB and silicones, suggest outgassing from

43

vinyl, floor tiles, ULPA filter potting compounds and other materials. As steps for mitigating cleanroom

outgassing, Camenzind recommends using carbon filters in the air recirculation system. The report also

details an outgassing study conducted by Balazs on the polypropylene shippers that are used for wafer

transport and storage. Balazs W.O. 00-02387 study heated a polypropylene shipper to 100°C for 30 min.

The outgassing results found antioxidant, di-tert-butyl-4-ethylphenol, and some hydrocarbons with a total

outgassing result of 11 ppm. In addition, the report mentions that the use of SafeSkin nitrile gloves

number 61013 had a noticeable organic residue during UPW cleaning and an alternative glove material

may be needed. While some of Camenzind’s recommendations would benefit from updating as

technologies and industry procedures mature, many of these ideas may be worthwhile for future

investigations into cleanroom operating procedures.

2.6.3 Outside Air Organic Analysis

JSC is located near large petrochemical plants, including ones that manufacture plastics less than 5

miles away. It is currently unknown how much residual background environmental contamination is

entering all curation laboratories. However, the JSC toxicology Lab in B37 analyzed outside and indoor

air samples in 2000. Results from air samples from the Genesis Room 1112, Meteorite lab, and outside

air near JSC building 31 north (B31N) are shown in figure 25 below.

Figure 25: JSC toxicology results in 2000 for Genesis lab, Meteorite lab, and JSC outside air.

The outside air sample is lower in all identified chemicals compared to both Meteorite and Genesis

laboratories. The cyclohexanone could be contributed to nylon-6 and the hexamethylcyclotrisiloxane

with silicone offgassing. However, it is unknown why these are elevated in the outside air sample;

possibly due to packaging of the sample prior to analysis. For Genesis and Meteorite labs, the use of IPA

wipes and Freon 113 for cleaning can be easily identified. Both labs also show elevated levels of silicone

offgassing from cleanroom sealants. Based on these results, outside air does not seem to contribute much

contamination to the curation laboratories. However, a full investigation of outside air contaminants has

never been conducted and this is the only known measurement of outside air at JSC.

GENESIS 1112 Room Air Meteorite Lab Room Air Outside Air JSC B31N

(ng/L) (ng/L) (ng/L)

FREON 12 * 6.58 *

ACETALDEHYDE 16.50 13.94 9.08

METHANOL 26.25 26.73 12.64

ETHANOL 45.93 68.36 3.16

ACETONE 13.13 38.88 6.10

ISOPROPANOL 293.20 362.35 *

PENTANE 4.51 7.14 *

FREON 113 * 97.92 *

HEXANE 3.24 4.26 *

TOLUENE 5.73 5.31 *

HEXANAL 4.87 6.06 *

HEXAMETHYLCYCLOTRISILOXANE 77.21 138.86 56.65

OCTAMETHYLCYCLOTETRASILOXANE 50.45 78.35 *

DECAMETHYLCYCLOPENTASILOANE 16.68 1119.99 *

TETRACHLOROETHENE * 77.50 *

CYCLOHEXANONE * 5.18 4.49

HEPTANAL * 6.96 *

BUTANAL 5.31 * *

Identified Chemicals

JSC B37 Toxicology 2000

44

3.0 ORGANIC CONTAMINATION BASELINE 2012 The 2012 organic contamination baseline study focused on testing the molecular organic contamination in

current working gloveboxes that house extraterrestrial samples. The study also focused on examining the

current cleaning protocols that are used for gloveboxes. Since this organic contamination baseline study

had limited funds, the project focused testing only on gloveboxes where historically there exists limited

data. In addition, future sample return missions will most likely use a type of isolation containment

system similar to a glovebox for sample containment beyond the use of a particulate reduced cleanroom.

Two gloveboxes were chosen for the study: the Advanced Curation Glovebox (ACG) and an Apollo 11

Lunar Curation Glovebox (LCG). The choice was made based on three measurement constraints: (1) test

the difference between a working glovebox after a cleaning compared to a cleaned glovebox without

samples, tools, and supplies; (2) the need to test current cleaning procedures with the difference of

cleaning a glovebox in-situ in the laboratory versus moving a glovebox for cleaning in Preclean; and (3)

the measurement of surface molecular organic contamination with methylene chloride could not be done

in a working glovebox due to possibility of contaminating lunar samples. The organic contamination

testing plan was to clean each glovebox with curatorial technical support procedure (TSP) 23.

Afterwards, the following tests would be done:

Liquid particle counts on UPW rinse water from cleaning

Scanning Electron Microscope (SEM) particle identification from UPW rinse filters from

cleaning

TD-GC-MS Analysis by Vertical Silicon Wafer Exposure

TD-GC-MS Analysis by Surface Silicon Wafer Exposure

TD-GC-MS Analysis by Absorbent Tube Exposure

Non-volatile residue Fourier Transform Infrared Spectroscopy (NVR/FT-IR) Analysis by

Methylene Chloride Surface Exposure (ACG ONLY)

Gas Chromatography Mass Spectroscopy (GC-MS) Analysis by Methylene Chloride Surface

Exposure (ACG ONLY)

The ACG was originally manufactured by Absolute Controls and outfitted by Oceaneering in 2000 for

testing advanced curation robotic sample handling techniques for future Mars sample return (figures 26 –

28). The glovebox was specifically designed to house a custom robotic arm for sample processing. The

ACG is currently housed in a positive pressure ISO class 5 cleanroom environment in B31, room 2022A.

The glovebox is constructed with electropolished 304 stainless steel, glass viewing windows, Viton seals,

and four Hypalon gloves. The glovebox is constantly purged at 50-75 scfh with house gaseous nitrogen

(GN2), a boil off of grade C LN2. During the testing, only supplies needed for the organic test were

located inside ACG and no work was done during exposure times. Possible organic material in ACG

included Viton gaskets and Hypalon gloves.

45

Figure 26: ISO class 5 cleanroom with ACG.

Figure 27: ACG inside the ISO class 5 cleanroom.

Figure 28: ACG after TSP 23 cleaning

The LCG is the original Apollo 11 Lunar processing cabinet #307-41 manufactured by the Stainless

Equipment Company in Englewood, Colorado, for the Lunar Curation Processing Laboratory in 1978 and

located in the Lunar Pristine Sample Laboratory (PSL) in JSC B31N in an ISO Class 6 cleanroom

environment (figures 29 and 30). The glovebox is constructed with 316L stainless steel (fine brush

polished), polycarbonate main window, glass PI viewing window, Viton seals, and six neoprene gloves.

Figure 29: PSL inside the Lunar laboratory, B31N. Figure 30: LCG located in the PSL inside an ISO

Class 6 cleanroom environment.

46

During all organic testing, the following items were situated inside the LCG in addition to tools needed

for organic sampling:

Nylon bags on tools and containers (not sealed in cabinet)

Teflon bags

One Teflon glove

Teflon disks

One Teflon floor brush

One small Teflon brush

Aluminum dust pan

Two scissors

4x4 inch x 2 mil Teflon sheets

Teflon Deutsch connector covers

One balance

One heat sealer

One adjustment platform (stage)

Stainless steel chisel, chipping ring and bottom, hammer

Stainless steel trays/one opened and others in sealed in nylon bags

Aluminum foil

Tweezers

Other tools still in sealed nylon bags

Aluminum containers

Four samples bagged in two Teflon bags each

One sample that was processed

Stainless steel containers with Teflon lids

1 cm and 1 inch direction cubes/black anodized

Stainless steel corner scale

Stainless steel 6 inch ruler

It should be noted that normal sample processing was conducted during all organic sampling inside the

LCG. This included the use of the heat sealer on Teflon bags. However, it should be noted that nylon

and polyethylene bags were not heated sealed during this testing to comply with standard laboratory

operating procedures. Possible organic material in LCG include Teflon (in the form of bags, jars, and

fittings), nylon tool bags, Viton gaskets, polycarbonate (Lexan) window, neoprene gloves, and silicone

rubber strip on the heat sealer.

The following are specific procedures and results from the organic testing. It is important to note that all

testing in the advanced curation glovebox was completed with no sample handling and minimal

disturbance to the glovebox. In comparison, all testing in the lunar processing cabinet was conducted

with maximum sample handling and working inside the glovebox. This was done to ensure a standard

baseline sampling of contaminates in a working glovebox.

47

3.1 Standard Glovebox Cleaning

TSP 23 (March 8, 2011 version) is the standard protocol for cleaning gloveboxes in all curation

laboratories with heated UPW (see Appendix III for full procedure). However, historically TSP 23 used

Oakite Liqui-DET (phosphates, amine, surfactants, and water miscible solvent) solution with mechanical

scrubbing, IPA, nitric acid, and Freon 113 as a degreaser and final rinse for glovebox cleaning (see

appendix II). Federal environmental policies on ozone depleting chemicals phased out

chlorofluorocarbon production from 1992 – 1995 and Freon 113 can no longer be used for cleaning at

JSC. Today, TSP 23 only uses UPW with a resistivity >18 MΩ, TOC < 5.0 ppb and heated to 70°C.

However, it was observed that the actual temperature was 52°C during cleaning of the ACG in Preclean.

For both gloveboxes, gaseous nitrogen flows at 50 scfh throughout the glovebox cleaning. The glove

ports are covered with Teflon and a slit is cut for PFA tube insertion with a PFA nozzle for rinsing. At

least three rinses are done with UPW rinse water being drained through a 47 mm diameter Millipore

mixed cellulose ester (MCE) 0.8 µm pore size filter paper for optical particle inspection for cleanliness.

For the LCG, lunar material would typically saturate the Millipore filter for the first or second rinse.

Therefore, before using the Millipore filters for final rinses, a 185 mm diameter Whatman grade 41

cellulose ashless 20 μm pore size filter paper is used to collect lunar sample material for proper

procedural disposal. After each rinse, the filter paper is observed under a Bausch and Lomb optical

stereomicroscope with a 4X objective lens to meet military standard (MIL-STD) 1246C cleanliness Level

50 (figure 31).

Level Particle Size (µm) Count per 1 ft2 Count per 0.1 m2 Counts per Liter

50 5 166 179 530

50 15 25 27.0 230

50 25 7.3 7.88 34

50 50 1.0 1.08 10 Figure 31: MIL-STD 1246C cleanliness Level 50.

The current TSP procedure states that glovebox rinses will continue “until no further significant decrease

in particles is attained and there are no more than 50 particles > 10 microns.” After the Millipore filter

paper meets this requirement, the glovebox is deemed cleaned and placed back into service.

Figure 32: LCG UPW cleaning. Figure 33: Stereomicroscope particle inspection

of filter paper from UPW rinse.

The cleaning history of the LCG is relatively well known. The glovebox was originally degreased in

1978 and periodically cleaned for over 30 years with various curation procedures and degreasing

48

chemicals. However, the cleaning history of the ACG is generally unknown. The glovebox has been

used by several JSC groups and has changed laboratories multiple times. Unfortunately, cleaning

certification and other cleaning documentation was not passed on between groups. Typically, the most

important cleaning history is in the transition from the glovebox manufacturing facility to a cleanroom.

While our team received verbal verification that the glovebox was initially degreased during the

procurement process, we do not have any documentation to verify this claim. Prior to this testing, the last

glovebox cleaning was on August 7, 2007, under curatorial order 14759 using TSP 23.

For this baseline study, the TSP 23 cleaning procedure remained the same for both glovebox cleaning.

The ACG and LCG also passed cleanliness MIL-STD Level 50 verification with optical inspection. The

LCG was cleaned in-place inside the Lunar laboratory ISO class 6 cleanroom. The ACG was located in

B31, room 2022A in an ISO class 5 cleanroom used for Mars studies. However, since this laboratory

does not have a local supply of UPW, the glovebox was transferred to curation Preclean B31 room 243 to

conduct TSP 23 and then moved back to room 2022A for organic testing. While in curation Preclean, the

glovebox was cleaned outside of the clean tent (Final Clean) area in room 243. The Final Clean area

particle filtered tent could not be used due to the large size of the glovebox. Therefore, while the inside of

the glovebox was under constant GN2 purge and all glove ports were sealed, the outside of the glovebox

was not contained inside a cleanroom. Prior to moving, the Hypalon gloves were removed and clean

Teflon was applied to each glove port. The move between room 2022A and 243 was orchestrated by

curation technicians working with JSC riggers to cleanly move the glovebox between the cleanroom and

Preclean facility. During each move, the glovebox was cleanly wrapped in clean polyethylene sheets and

the move was done quickly to mitigate the down time of being under constant GN2 purge.

3.2 Liquid Particle Counts from Glovebox Cleaning Glovebox drain samples of UPW from the TSP 23 cleaning were collected in Teflon bottles for particle

counter analysis for comparison with the optical particle inspection. Each UPW sample was analyzed by

a HIAC Liquid Syringe Sampler and Particle Counter in the Genesis Advanced Precision Cleaning

Laboratory ISO Class 4 cleanroom. During TSP 23, UPW rinses were stopped once the optical

stereomicroscope particle observation reached a Level 50 cleanliness standard. For both gloveboxes, two

rinses and a final rinse were collected for analysis. In addition, a UPW baseline control was collected

before UPW cleaning. The results for particle counts for each cleaning are shown in figures 34 and 35.

Each sample was run on the particle counter three times and the results in the table are the average of

these counts. UPW from the Genesis lab was used as a control before and after sample runs to check the

accuracy of the particle counter. The particle counts are given in particle size per 10 ml of UPW. For

comparison, the MIL-STD Level 50 has also been provided in the tables below.

49

Figure 34: ACG UPW particle counts from TSP 23 cleaning.

Figure 35: LCG UPW particle counts from TSP 23 cleaning.

The particle count results show that the LCG is much cleaner than the ACG in the lower particle sizes.

While both particle count results show that each glovebox passes MIL-STD Level 50 at 25 µm size

particles for the final rinse, both gloveboxes fail Level 50 at 5 µm particle size diameter. This can be

expected when it is difficult to resolve particles < 25 µm in diameter using a low magnification optical

stereomicroscope for particle counts during TSP 23. In addition, the optical microscope technique also

allows for the potential for human error. The ACG results show that rinse 2 is lower than the final rinse

for particle sizes < 10 µm. Particle count loads at 1 µm particle size diameter also show a dramatic

difference between rinses, which is not normal. Usually, a downward trend is seen with lowering particle

counts with more rinses until a plateau is reached. A possible explanation is that some type of

contamination is still adhering to the glovebox material and not ablating evenly during UPW rinsing.

This could potentially mean that the ACG glovebox was never degreased from original manufacturing.

3.3 Scanning Electron Microscope Particle Identification from Glovebox Cleaning Particle counts provide a quick and inexpensive measure for the amount of particle contamination and

effectiveness of cleaning. However, the identity of the particles is largely unknown. Therefore, the filter

paper used during TSP 23 UPW cleaning for optical particle inspections were analyzed with a SEM for

Genesis

After

Control

1 27 331.33 104526 4412 13290 45

3 1 14 21167 533.33 1806.8 3

5 1 5.67 6503.33 159 707.75 0 5.3

10 1 1.67 492.33 19 26.75 0

25 0 0.33 4.33 0.33 0.5 0 0.34

50 0 0 0 0 0.25 0

100 0 0 0 0 0.25 0

150 0 0 0 0 0.25 0

Note: all counts are averages of measurements.

Advanced Curation Glovebox TSP 23 Cleaning

UPW Particle Count per 10 ml

Particle

Size (µm)

Genesis

Before

Control

PreClean

UPW

Baseline Rinse 1 Rinse 2

Final

Rinse

MIL-

STD

Level

1 2 886.4 3622.67 2005.33 1246.6 4

3 0 54.8 749.67 394.33 128.8 0

5 0 15.2 340.33 185.67 40.2 0 5.3

10 0 1.6 101.33 47 6.2 0

25 0 0 22 0.67 0.6 0 0.34

50 0 0 19.33 0 0.4 0

100 0 0 18.67 0 0.4 0

150 0 0 17 0 0.4 0

Note: all counts are averages of measurements.

Lunar Curation Glovebox TSP 23 Cleaning

UPW Particle Count per 10 ml

Particle

Size (µm)

Genesis

Before

Control

Lunar

UPW

Baseline Rinse 1 Rinse 2

Final

Rinse

MIL-STD

Level 50

Genesis

After

Control

50

particle identification. A JEOL JSM-7600F Field Emission Scanning Electron Microscope (FE-SEM)

was used to survey 392 particles with over 450 spot analyses with a low angled backscatter electron

(LABe) detector. The final rinse Millipore filters were analyzed for both LCG and ACG TSP 23 cleaning

rinses. The 47 mm diameter Millipore MCE 0.8 µm pore size filter paper was cut to fit onto a 1 cm

diameter SEM stub and carbon coated. The MCE filter material is a combined cellulose acetate and

cellulose nitrate matrix. In addition, a 185 mm diameter Whatman grade 41 cellulose ashless 20 μm pore

size filter paper that was used on the first LCG rinse was also analyzed for particle identification of initial

large particle release.

A systematic survey of the subdivided sample searched for particles trapped by the filter. Each particle

had a SEM image taken as well as a chemical spectrum. On more complex particles, more than one

spectrum was taken for chemical identification. After a particle was identified, similar particles with

similar spectrum were placed into possible identified material groups and counted. The results are shown

in figures 36 to 41 with major groups of particles. Each particle size was also given an average size

diameter and each group was given a size range and average size of the group. The particle percentage

can be used to compare with the UPW particle count analysis to give a relative contamination load of

each glovebox. In addition, a small sample of different types of organic particles images and spectra are

shown from this investigation in figures 42-47.

Figure 36: LCG SEM particle identification on 20 micron pore size filter.

Possible Identified

Material Groups

Particle

Count Particle %

Size

Range

(µm)

Average

Diameter

Size (µm)

Aluminum Silicate 2 3.51% 100 100

Calcium Carbonate 2 3.51% 25 to 50 38

Fluorine 1 1.75% 100 100

Iron Oxide 12 21.05% 20 to 300 77

Iron Sulfate 1 1.75% 12 12

Lunar Geologic Material 25 43.86% 5 to 100 29

Lunar Geologic Ilmenite 1 1.75% 20 20

Stainless Steel 3 5.26% 5 to 120 15

Organic Compound 9 15.79% 5 to 50 26

Unknown 1 1.75% 200 200

Particle Count Total 57 100.00%

Whatman grade 41 cellulose ashless 20 μm pore size filter

Lunar Curation Glovebox SEM Particle Identification

51

Figure 37: Chart for LCG SEM particle identification on 20 micron pore size filter.

Figure 38: LCG SEM particle identification on 0.8 micron pore size filter.

Aluminum Silicate3% Calcium Carbonate

3%Fluorine

2%

Iron Oxide21%

Iron Sulfate2%

Lunar Geologic Material

44%

Lunar Geologic Ilmenite

2%

Stainless Steel5%

Organic Compound16%

Unknown2%

Lunar Curation GloveboxSEM Particle Identification

Whatman 20 µm Filter

Possible Identified

Material Groups

Particle

Count Particle %

Size

Range

(µm)

Average

Diameter

Size (µm)

Aluminum 1 1.12% 25 25

Aluminum Oxide 1 1.12% 12 12

Iron Oxide 1 1.12% 5 5

Stainless Steel 23 25.84% 2 to 10 5

Lunar Geologic Material 24 26.97% 2 to 15 6

Lunar Geologic Ilmenite 7 7.87% 3 to 8 8

Organic Compound 27 30.34% 2 to 100 16

Hydrocarbon 1 1.12% 10 10

Silicone 4 4.49% 4 to 8 6

Particle Count Total 89 100.00%

Lunar Curation Glovebox SEM Particle Identification

Millipore MCE 0.8 µm pore size filter

52

Figure 39: Chart for LCG SEM particle identification on 0.8 micron pore size filter.

Figure 40: ACG SEM particle identification on 0.8 micron pore size filter.

Aluminum1%

Aluminum Oxide1%

Iron Oxide1%

Stainless Steel26%

Lunar Geologic Material

27%

Lunar Geologic Ilmenite

8%

Organic Compound30%

Hydrocarbon1%

Silicone5%

Lunar Curation GloveboxSEM Particle Identification

Millipore 0.8 µm Filter

Possible Identified

Material Groups

Particle

Count Particle %

Size

Range

(µm)

Average

Diameter

Size (µm)

Aluminum 4 1.63% 3 to 10 6

Calcium Carbonate 6 2.44% 1 to 5 3

Copper Sulfate 4 1.63% 1 to 5 4

Iron Oxide 17 6.91% 3 to 30 9

Iron Phosphate 2 0.81% 3 to 10 2

Iron Sulfide 2 0.81% 2 to 2 7

Potassium carbonate 1 0.41% 5 5

Geologic Silicate Mineral 51 20.73% 1 to 25 7

Silver Cadmium Oxide 3 1.22% 5 to 10 8

Stainless Steel 16 6.50% 0.5 to 10 4

Fluorosilicone 10 4.07% 1 to 25 6

Hydrocarbon 5 2.03% 5 to 50 24

Organic Compound 95 38.62% 0.5 to 100 18

Silicone 30 12.20% 1 to 25 6

Particle Count Total 246 100.00%

Millipore MCE 0.8 µm pore size filter

Advanced Curation Glovebox SEM Particle Identification

53

Figure 41: Chart for ACG SEM particle identification on 0.8 micron pore size filter.

Figure 42: SEM image and chemistry of unknown organic particle with a carbon signature.

Aluminum2%

Calcium Carbonate

2%

Copper Sulfate2%

Iron Oxide7%

Iron Phosphate1%

Iron Sulfide1%

Potassium carbonate0%

Geologic Silicate Mineral

21%

Silver Cadmium Oxide

1%

Stainless Steel6%

Fluorosilicone4%

Hydrocarbon2%

Organic Compound39%

Silicone12%

Advanced Curation GloveboxSEM Particle Identification

Millipore 0.8 µm Filter

54

Figure 43: SEM image and chemistry of unknown organic fiber with carbon and oxygen signature.

Figure 44: SEM image and chemistry of unknown organic particle with carbon and oxygen signature.

Figure 45: SEM image and chemistry of unknown organic particle with carbon and oxygen signature.

55

Figure 46: SEM image and chemistry of unknown organic particle/fiber with carbon, nitrogen, and oxygen

signature.

Figure 47: SEM image and chemistry of unknown organic particle with silicone, oxygen, and carbon

signature; possibly silicone.

The large Whatman LCG filter shows that most of the geologic material was removed from the glovebox

on the first few rinses and was reduced in quantity in the final rinse. The Lunar geologic material was

mostly plagioclase, pyroxene, olivine, K-feldspar, and ilmenite. Aluminum, aluminum silicate, aluminum

oxide, iron sulfate, and fluorine could possibly be geologic in nature. However, some could have been

introduced by cross-contamination from the lab as well as the calcium carbonate found. In both LCG

analyses, the iron oxide is probably geologic in origin, but could also be from the steel in the glovebox.

The organic compounds (figures 42 to 47), silicone, and hydrocarbons are probably from laboratory

contamination sources. These organic particles could come from the polycarbonate window, neoprene

gloves, Viton seals, and numerous nylon and Teflon bags used in the glovebox. In addition, the heat seal

has a silicone strip.

The ACG final rinse filter contained more organic compounds, silicone, fluorosilicone, and hydrocarbons

than the LCG samples. Since the ACG processed terrestrial geologic materials, the sample contained a

wide range of silicate minerals, calcium carbonate, copper sulfide, iron phosphate, iron sulfide, potassium

carbonate, and aluminum. The iron oxide most likely is from the steel in the glovebox and/or could be

sample related. The silver cadmium is most likely from the robotic arm electronics that was used inside

the glovebox. The two graphs in figure 48 and 49 show a percentage breakdown of organic, geologic

56

sample material, and metal contamination from the glovebox. Organic contamination is much greater on

the ACG than the LCG. If the particle count data for 1 micron particle size is applied to the organic

particle identified, the LCG final rinse has about 448 organic particles/10 mL and ACG final rinse has

about 7575 organic particles/10 mL. This higher organic load in the ACG could be interpreted that the

glovebox was never thoroughly degreased. Other organic sources may include Hypalon gloves and Viton

gaskets. Based on the SEM images from this study, it is difficult to directly relate the morphology of the

particle to specific organic contamination sources.

Figure 48: General chart for LCG SEM particle

identification. Figure 49: General chart for ACG SEM particle

identification.

3.4 Vertical and Surface Wafer Exposure Thermal Desorption Gas Chromatography Mass Spectroscopy Analysis Air Liquide Balazs Nanoanalysis was contracted for molecular organic analysis in both gloveboxes in

order to have comparable results to past glovebox investigations. This is the same contractor that has

been used since 1998 in JSC curation for organic and inorganic testing. The vertical exposure of 8” or 6”

diameter ultra-pure silicon semiconductor wafers for 24 hours and subsequent TD-GC-MS analysis has

been historically done at JSC Curation for airborne contamination. For better comparison with previous

data sets, we selected the same laboratory sampling procedure for the 2012 organic testing. However, a

new sampling technique was added to attempt a better understanding of organic contamination adhering

to the surface of the glovebox. This was to expose a second set of silicon wafers, oriented face down, to

the surface of the glovebox. ACG and LCG were both sampled with the same method. However, a 6”

diameter silicon wafer instead of a standard 8” diameter wafer was used for the ACG due to the size of

the glove ports for sample insertion.

For each test in ACG and LCG, two pairs of the pre-baked silicon wafers were sent to JSC. The first set

of wafers was exposed vertically for 24 hours. The second set of wafers was also simultaneously exposed

vertically for 24 hours and then placed onto the surface of the glovebox for the last 15 min. to attempt to

measure surface contamination. The pre-cleaned wafer samples came packaged in three layers of pre-

baked aluminum foil and were sandwiched face to face (polished mirror side together). For the LCG, the

wafers were introduced to the glovebox through the standard antechamber pass-through door. These

wafers were exposed to a working lunar glovebox during testing. For the ACG, the 6” wafers were

introduced quickly into the glovebox by the removal of one of the 8” glove ports, since the ACG does not

have a sample pass-through door. In contrast to the working lunar glovebox, the ACG was undisturbed

throughout the sampling. After sampling, the sampled wafers were wrapped face-to-face in three layers

Metals29%

Organics36%

GeologicMaterial

35%

Lunar Curation GloveboxSEM Particle Identification

Millipore 0.8 µm Filter

Metals19%

Organics57%

GeologicMaterial

24%

Advanced Curation GloveboxSEM Particle Identification

Millipore 0.8 µm Filter

57

of pre-baked aluminum foil and shipped back to Balazs for TD-GC-MS analysis along with a shipping

control wafers that were never opened (see figures 50 to 54).

Figure 50: Lunar material being processed inside

LCG during testing. Figure 51: 8” silicon wafers exposed during

organic testing inside the LCG.

Figure 52: 6” silicon wafer surface exposure. Figure 53: 6” silicon wafer vertical exposure in

the ACG.

Figure 54: Silicon wafer handling during the ACG organic testing.

58

Balazs supplied JSC with a report and specified the analytical procedure for obtaining the results. At

Balazs, the silicon wafers were heated in a GL Sciences SWA-256 full wafer desorption system in a

continuously flowing stream of ultra-high purity helium. The sample chamber temperature was increased

from ambient to 400°C in 15 min. and maintained 400°C for an additional 15 minutes. Stainless steel

sampling tubes containing proprietary adsorbents at near-ambient temperature were used to capture

organic compounds from one side of wafer surface. These sampling tubes were then analyzed by TD-

GC-MS per Balazs procedure "SEMI MF 1982-1103 Method-B". The GC was equipped with a non-polar

poly (dimethylsiloxane) phase capillary column. The GC was programmed with an initial temperature to

maintain 35°C for 3.5 min. and then increase at a rate of 10°C/min. to 280°C followed by maintaining the

final temperature of 280°C for 10 min. Helium was used as the carrier gas for the GC-MS and an internal

standard, toluene-d8, was added to each sampling tube during the analysis.

The results were reported in units of ng/cm2, which was based on the surface area of one side of the

wafers and are expressed by the equivalent n-hexadecane external standard value. Labeled

chromatograms were included for each sample. The results were expressed both in terms of the total

organics in three different ranges (based roughly upon boiling point) and as individual compounds

detected at concentrations above the reporting limit. Identification of each compound detected was first

attempted by searching 275,000 mass spectra in a Wiley library. In cases where no matches were found,

the Balazs analyst interpreted the mass spectra to give best estimate of the most probable compound or

class of compounds. The organic compounds were classified into three boiling ranges, low-boiling (C7 –

C10), medium-boiling (>C10 – C20) and high-boiling (>C20), based on comparisons with the retention times

of a C7 – C28 n-hydrocarbon external standard. Semiquantitated amounts of the organic compounds in

each boiling range were calculated by using the integrated total ion count (TIC) of that boiling range and

the response factor for an n-hexadecane external standard. For semiquantitated compounds, amounts of

individually identified compounds were estimated using TIC area of that compound and the response

factor of an n-hexadecane external standard. The following results were obtained in figures 55 to 60.

59

Figure 55: LCG Balazs organic wafer test results.

Figure 56: LCG Balazs organic wafer TD-GC-MS plot for vertical wafer exposure.

Hydrocarbons

Control

Wafer

(ng/cm²)

Vertical

Exposure

(ng/cm²)

Surface

Exposure

(ng/cm²)

Low boilers C7-C10 * * 0.2

Medium boilers >C10-C20 * 1.8 2.5

High boilers >C20 * 0.1 0.2

Sum >= C7 * 1.9 2.9

Identified Compounds

Diethylformamide * * *

Diethylacetamide * * *

Alkyl amine * * *

2-Butoxyethyl acetate * * *

Octafluoropentanal(m/z:51,69,100,131,151,181,200,231,281) * * *

2-Cyclohexen-1-one, 3,5,5-trimethyl- * 0.3 0.3

Dibutylformamide * 0.2 0.2

Cyclo(Me2SiO)6 * 0.2 0.2

2,6-di-tert-Butylquinone * * *

Cyclo(Me2SiO)7 * * *

Cyclo(Me2SiO)8 * * 0.1

Cyclo(Me2SiO)9 * 0.2 0.3

Dibutyl phthalate * * 0.1

Cyclo(Me2SiO)10 * 0.1 0.2

Siloxane * 0.1 0.1

* Recording Limit = < 0.1 ng/cm²

Lunar Curation Glovebox

60

Figure 57: LCG Balazs organic wafer TD-GC-MS plot for surface wafer exposure.

Several identified chemicals above reporting limit were found for the LCG. The solvent isophorone (2-

cyclohexen-1-one, 3,5,5-trimethyl-) was detected and is typically used in printing inks, paints, lacquers,

adhesives, copolymers, coatings, finishings, and pesticides. In addition, it can be used as a chemical

intermediate and as an ingredient in wood preservatives and floor sealants. Dibutylformamide (DBF) is

an additive or reducing agent used in manufacturing of polymers, rubbers, medicines, herbicides, flame

retardants in fabrics, solvents, inks, and photo paper. DBP is a common plasticizer used in adhesives,

solvents and inks. The LCG results show elevated levels of silicones: cyclo(Me2SiO)6, cyclo(Me2SiO)8,

cyclo(Me2SiO)9, cyclo(Me2SiO)10, and siloxane. These can be found in silicone adhesives and

cleanrooms sealants. However, the silicones may also be from the heat sealer that was used to seal Teflon

bags. The heat sealer has a known silicone rubber strip that clamps down on the bag while heating the

material.

61

Figure 58: ACG Balazs organic wafer test results.

Hydrocarbons

Control

Wafer

(ng/cm²)

Vertical

Exposure

(ng/cm²)

Surface

Exposure

(ng/cm²)

Low boilers C7-C10 * 0.4 0.4

Medium boilers >C10-C20 * 7.1 9.6

High boilers >C20 * 1.1 1.8

Sum >= C7 * 8.6 11.8

Identified Compounds

Dibutylamine * * *

N-Formylpiperidine * * 0.1

2-(2-Butoxyethoxy)ethanol * 0.6 1

Caprolactam * 0.2 0.6

Tripropylene glycol * * *

Dibutylformamide * * 0.1

N,N-Dibutylacetamide * * *

Texanol * * *

Dimethyl phthalate * * *

Diisopropyl adipate * * *

2,6-di-butyl-2,5-cyclohexadiene-1,4-dione * * *

2,6-di(t-butyl)-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one * * *

Cyclo(Me2SiO)7 * * *

Diethyl phthalate * 0.2 0.3

TXIB * 0.3 0.3

Piperidine, 1,1'-carbonylbis- * * *

Cyclo(Me2SiO)8 * 0.3 0.5

Tri(2-chloroethyl) phosphate * 0.2 0.2

Benzenesulfonamide, N-butyl- + 3,5-di-tert-Butyl-4-hydroxybenzaldehyde * * *

Benzenesulfonamide, N-butyl- * * *

Isopropyl Myristate * * *

Diisobutyl phthalate * 0.1 0.1

Cyclo(Me2SiO)9 * * 0.1

Dibutyl phthalate * 0.5 0.6

C17-C22 Hydrocarbon * * 0.1

* Recording Limit = < 0.1 ng/cm²

Advanced Curation Glovebox

62

Figure 59: ACG Balazs organic wafer TD-GC-MS plot for vertical wafer exposure.

Figure 60: ACG Balazs organic wafer TD-GC-MS plot for surface wafer exposure.

63

The identified chemicals above reporting limit for the ACG are N-formylpiperidine and 2-(2-

butoxyethoxy) ethanol, which are both solvents. Caprolactam was found and is usually associated with

nylon-6 bags. DBF, a rubber/polymer additive, was also found. Several plasticizers above reporting

limits included DEP, TXIB, DBP, and DIBP. Tri(2-chloroethyl) phosphate can be associated with flame

retardant in plastics. Silicones found were cyclo(Me2SiO)8 and cyclo(Me2SiO)9 along with C17 – C22

hydrocarbons.

3.5 Air Absorbent Thermal Desoprtion Gas Chromatography Mass

Spectroscopy Analysis The determination of organics in air was also completed through Air-Liquide Balazs Analytical Services.

Balazs provided a sampling kit to JSC curation that contained a sample pump and two stainless steel

sample tubes packed with multiple beds of proprietary adsorbents. For both the ACG and LCG, a clean

128 mm long, ¼” diameter stainless steel GN2 tube was connected directly from the main glovebox

chamber to the stainless steel absorbent sampling tube. The other end of the absorbent sampling tube was

then connected to a Gilian LFS-113 low flow sampling pump set at a flow rate of 100 mL/min (see

figures 61 to 63). The sampling pump was run for exactly 6 hours while the glovebox GN2 flow rate was

set at a nominal 50 scfh. Afterwards, the absorbent sampling tube was sealed at both ends with the

original stainless steel compression fitted ends and then wrapped in clean baked-out aluminum foil for

shipping to Balazs for TD-GC-MS analysis. In addition, a shipping control sampling tube was sent with

the kit and was never opened at JSC.

Figure 61: Location of adsorbent tube attachment

to main chamber of the ACG. Figure 62: Location of adsorbent tube attachment

to main chamber of the LCG.

64

Figure 63: Gilian sampling pump and adsorbent tube for collecting organics in air.

The following experimental set-up for TD-GC-MS was reported by Balazs. At Balazs, the GC used a

non-polar poly (dimethylsiloxane) phase capillary column. The GC was programmed with an initial

temperature to maintain 35°C for 3.5 min. and then increase at a rate of 10°C/min. to 280°C followed by

maintaining the final temperature of 280°C for 10 min. Helium was used as the carrier gas for the GC-

MS and an internal standard, toluene-d8, was added to each sampling tube during the analysis. This test

method was designed to analyze semi-volatile organic compounds in the boiling point range of n-heptane

(boiling point approximately 100°C) to n-octacosane (boiling point approximately 430°C). Identification

of each compound detected was first attempted by searching a Wiley library of 275,000 mass spectra. In

cases where no matches were found, mass spectra were interpreted by the Balazs analyst to give best

estimate of the most probable compound or class of compounds.

The results were reported as n-decane in units of ng/L along with labeled chromatograms for each sample.

The organic compounds are classified into three boiling ranges, low-boiling (C7 – C10), medium-boiling

(>C10-C20) and high-boiling (>C20), based on comparisons with the retention times of a C7 – C28 n-

hydrocarbon external standards. Semiquantitative amounts of the organic compounds in each boiling

range are calculated by using the integrated TIC of that boiling range and the response factor for an n-

decane external standard. Amounts of individually identified compounds were estimated using TIC area

of that compound and response factor of n-decane external standard. The following results were given for

the ACG and LCG in figures 64 and 65.

65

Figure 64: LCG Balazs results for adsorbent tube. Figure 65: ACG Balazs results for adsorbent tube.

The determination of organics in air provides a better understanding of the organic cleanliness of the

gaseous nitrogen environment and sometimes provides a better VOC load. Unlike the silicon wafers,

which collect airborne particles well, the absorbent tube should be better at collecting VOCs in the

gaseous nitrogen environment. Conversely, silicon wafers should be better suited for collection of

suspended particles. Compared with the silicon wafer tests, the absorbent tubes also provide a better

insight into the hydrocarbon load inside the glovebox’s main sample processing chamber.

For the identified organic compounds, the LCG has 0.2 ng/L of cyclo(Me2SiO)4 that can be representative

of silicone outgassing. The LCG results also show 0.3 ng/L of chlorodecane, which is a plasticizer that is

indicative of outgassing of a rubber. The most likely source for the presence of cyclo(Me2SiO)4 and

chlorodecane is the use of a heat sealer, which has a silicone rubber strip. Both ACG and LCG results

detected hydrocarbons >C7. In comparison, the hydrocarbon load in the LCG is much lower than the

ACG, which is almost four times larger. This difference is not understood.

It was proposed that one possibility of the difference in hydrocarbon load could be indicative of the

cleanliness level of the nitrogen piping infrastructure between B31 and B31N. In July 2013, a

determination of organics of the GN2 supply lines was conducted with Balazs. The LCG, AGC, and a

B31, room 215 nitrogen supply lines were tested. B31, room 215 is the future planned location of the

OSIRIS-REx Laboratory and the supply line closest to the lab entry door was tested. Each supply line

was fitted with two ¼” stainless steel adsorbent tubes with a flow rate of 100 ml/min. for 24 hours. The

adsorbent sample tubes and control tubes were sent back to Balazs for TD-GC-MS analysis. All three

locations resulted in no organic compounds found and all hydrocarbon loads were below the reporting

limit of < 0.1 ng/L for >C7 (figure 66). The same Balazs TD-GC-MS analysis was also conducted on

April 12, 2004, for the GN2 supply in Genesis laboratory room 1107 and mechanical room 1108 in

B31N. It should be noted that this testing was done prior to the installation of a new LN2 tank in 2006.

The results also reported no organics compounds were found and all hydrocarbon loads were below the

reporting limit of < 0.1 ng/L for >C7 (figure 24). Therefore, the B31 and B31N nitrogen supply lines are

not the cause for elevated organic levels in LCG and ACG. The two separate data points also suggest that

Hydrocarbons

Control

Blank

(ng/L)

TD-GC-MS

Results

(ng/L) Hydrocarbons

Control

Blank

(ng/L)

TD-GC-MS

Results

(ng/L)

Low boilers C7-C10 * 1.2 Low boilers C7-C10 * 0.6

Medium boilers >C10-C20 * 3.8 Medium boilers >C10-C20 * 18.8

High boilers >C20 * * High boilers >C20 * 0.1

Sum >= C7 * 5 Sum >= C7 * 19.5

Identified Organic Compounds Identified Organic Compounds

Cyclo(Me2SiO)3 * * Methyl methacrylate * *

Ethylbenzene * * Cyclo(Me2SiO)3 * *

m,p-Xylene * * Cyclo(Me2SiO)4 * *

o-Xylene * * Limonene * *

Cyclo(Me2SiO)4 * 0.2 C3 benzene * *

Cyclo(Me2SiO)5 * * C10-C14 Hydrocarbon * 0.2

Methylnaphthalene * * C16-C20 hydrocarbon * 16.8

Chlorodecane * 0.3

C12-C16 Hydrocarbons * 0.3

Lunar Curation Glovebox

* Reporting Limit = < 0.1 ng/L

Advanced Curation Glovebox

* Reporting Limit = < 0.1 ng/L

66

in-house nitrogen does not seem to be a general source for any organic contamination in curation

laboratories.

Figure 66: Balazs TD-GC-MS results for GN2 supply organic testing in 2013.

The TD-GC-MS analysis adsorbent results can also be used to classify the glovebox air cleanliness

according to ISO-AMC air cleanliness class; ISO 14644-8 (figure 67). For example, -12 is the cleanest at

0.001 ng/m3 Total Volatile Organic Compounds (TVOC) concentration. Based on these TD-GC-MS

results, the LCG total hydrocarbons = 5 ng/L = 5000 ng/m3 and has an ISO-AMC = – 5 (10

4 ng/m

3). For

the ACG, total hydrocarbons = 19.5 ng/L = 19500 ng/m3 and has an ISO-AMC = – 4 (10

5 ng/m

3).

Figure 67: ISO-AMC air cleanliness class; ISO 14644-8.

Control

Blank

(ng/L)

GN2 Supply

OSIRIS-REx

Lab B31 R215

TD-GC-MS

Results

(ng/L)

GN2 Supply

LCG Lunar

Lab TD-GC-

MS Results

(ng/L)

GN2 Supply

ACG B31

R2022A

TD-GC-MS

Results

(ng/L)

Low boilers C7-C10 * * * *

Medium boilers >C10-C20 * * * *

High boilers >C20 * * * *

Sum >= C7 * * * *

Identified Organic Compounds

None * * * *

July 2013 Testing

* Reporting Limit = < 0.1 ng/L

Hydrocarbons

ISO-AMC Class TVOC Concentration

(ng/m3)

0 109

– 1 108

– 2 107

– 3 106

– 4 105

– 5 104

– 6 1000

– 7 100

– 8 10

– 9 1

– 10 0.1

– 11 0.01

– 12 0.001

67

3.6 Surface Methylene Chloride Exposure Non-volatile Residue/Fourier Transform Infrared Spectroscopy and Gas Chromatography Mass Spectroscopy Analysis In consultation with Balazs, a new methodology was attempted to better understand the organic

contamination adhering to the surface of the glovebox in addition to the surface wafer exposure. The new

technique would use a highly pure solvent, methylene chloride, to dissolve any surface contamination.

The exposed methylene chloride would then be tested by standard GC-MS and NVR/FT-IR analysis.

Balazs shipped to JSC pure methylene chloride in a glass vial along with a glass syringe. Methylene

chloride was applied to the surface for a few seconds and immediately reacquired with the syringe needle

and emptied into a clean vial for shipment back to Balazs (see figures 68 and 69). Two samples were

taken for each analytical method. Since methylene chloride could potentially contaminate lunar material

inside the LCG, only the ACG was tested by this method.

Figure 68: Application of methylene chloride to

the surface of the ACG with glass syringe. Figure 69: Collection of methylene chloride to the

surface of the ACG with glass syringe.

At Balazs, the methylene chloride sample was completely concentrated for NVR/FT-IR analysis. The

residue was weighed and transferred to a metal mirror for reflectance mode FT-IR analysis utilizing

Nicolet 6700 FT-IR system coupled to Continuum FT-IR microscope. The spectra were collected at 8

cm-1

resolution with 64 scans. Background spectra were collected on a clean area of the mirror. The

control sample was 0.004 mg and the ACG sample was 0.158 mg. Below is the spectrum for the FT-IR

analysis (figure 70).

68

Figure 70: ACG Balazs plot for NVR/FT-IR results.

The infrared spectrum collected on the blank exhibited no significant infrared absorption bands. The

infrared spectrum collected on the ACG sample residue exhibited C-H stretching absorption bands at

2958, 2927, and 2856 cm-1

, carbonyl stretching absorption band at 1732 cm-1

, aromatic ring mode

absorption bands at 1600 and 1580 cm-1

, C-H bending absorption band at 1461 cm-1

, C-H umbrella mode

absorption band at 1379 cm-1

, C-C-O stretching absorption band at 1287 cm cm-1

, and O-C-C stretching

absorption band at 1126 cm-1

. In addition, C-H in-plane bending absorption band 742 cm cm-1

was found

and was interpreted as typical for a dialkyl phthalate; e.g. diheptyl or dioctyl phthalate (DOP). The

NVR/FT-IR results also show the presence of aromatic hydrocarbons. The carbonyl can be interpreted as

indicative of some organometallic complexes. However, the interpretation of the presence of dialkyl

phthalate is a common group of chemicals associated with plasticizers and mainly found in the

manufacturing of PVC. This interpretation of the results matches closely with the GC-MS analysis

below.

At Balazs for GC-MS, the second sample of exposed methylene chloride was concentrated to a minimum

amount and an internal standard (Hexadecane) was added for the GC-MS analysis. A HP 7890 GC with a

5975C quadrupole Mass Selective Detector (MSD) was equipped with a non-polar poly

(dimethylsiloxane) phase capillary column for the analysis. The GC was programmed to begin with an

initial temperature 40°C for 3 min. and then increased at a rate of 20 °C /min. to 280°C and held at 280°C

for 30 min. The injection port temperature was 280°C and the sample volume injected was 1.0 µL. Each

compound passed down the GC column at a characteristic rate. As each compound exited the CG, it

entered the MSD where it was ionized using electron impact ionization (70 eV). The MSD collected a full

mass spectrum (10-700 amu) approximately once per second. Each identified compound detected was

first searched using the Wiley library of 275,000 mass spectra. In cases where no matches were found,

the analyst interpreted the mass spectra to give best estimate of the most probable compound or class of

compounds. The results are below in figure 71.

69

Figure 71: ACG Balazs plot for GC-MS results.

Four chemicals were found by GC-MS. 2-Chloro-Ethanol, Phosphate (3:1) or TCEP – C9H15O6P • HCl is

commonly used as a reducing agent in biochemistry and in detergents. TCEP has also been widely used

as a flame retardant and manufacturing of PVC vinyl, electronics, adhesives, upholstery, carpeting,

rubber, plastics, paints, and varnishes. +N-Butylbenzenesulphonamide (NBBS) – C10H15NO2S is widely

used as a plasticizer in industrial chemicals and drugs. NBBS also has antifungal properties and was

commonly used on agricultural fields for over 30 years and is now a common contamination in ground

water supplies. In addition, NBBS is fairly common building block for industrial chemicals and drugs.

Bis(2-ethylhexyl) phthalate (DOP or di-2-ethylhexyl phthalate (DEHP) – C24H38O4) is a common

plasticizer in many plastics manufacturing and most common in the outgassing of PVC type materials.

DEHP is widely found in the environment and municipal water supplies in low levels from manufacturing

of PVC. 1, 2-benzenedicarboxylic acid, dinonyl ester– C26H42O4 or commonly called dinonyl phthalate

(DNP) is used primarily as a low efficiency plasticizer for PVC to impart flexibility. DNP can also be

found in many types of vinyl from automotive to electrical wiring as well as uses as an additive in

lubricating oils.

70

4.0 SUMMARY

Hydrocarbons, plasticizers, solvents, silicones, and rubbers are the majority of organic contamination

found in JSC astromaterials curation cleanrooms and gloveboxes. A list of all organic compounds found

in JSC curation (B31 and B31N) to date has been provided in Appendix I. After standard UPW cleaning

of the ACG and LCG, both gloveboxes showed relatively low levels of organics when compared to

standard laboratories. Hydrocarbon loads (> C7) ranged from 1.9 to 11.8 ng/cm2 for TD-GC-MS wafer

exposure analyses and 5.0 to 19.5 ng/L for TD-GC-MS adsorbent tube exposure (ISO-AMC air

cleanliness class – 4 and – 5 respectively). Plasticizers included < 0.6 ng/cm2 of DBP, DEP, TXIB, and

DIBP. Silicones included < 0.5 ng/cm2 of cyclo(Me2SiO)x (x = 6, 8, 9, 10) and siloxane. Solvents

included < 1.0 ng/cm2 of 2-cyclohexen-1-one, 3,5,5-trimethyl- (isophorone), N-formylpiperidine, and 2-

(2-butoxyethoxy) ethanol. In addition, DBF, rubber/polymer additive was found at < 0.2 ng/cm2 and

caprolactam, nylon-6 at < 0.6 ng/cm2. All other identified organic compounds were below a reporting

limit of < 0.1 ng/cm2. It is difficult to trace specific sources of organic contamination given that these

organic additives and compounds are used in many different types of manufactured products. In some

cases, it is unclear whether some of these detected organics are from inside the lab or from the

background environment (e.g., common plasticizers released into the Houston air and not filtered through

the cleanroom air handling and filtration system). While the one data point from JSC Toxicology

measurements in 2000 suggests that the background environment may not contribute much

contamination, if any, the subject should be further explored. More importantly, additional individual

laboratory material organic testing is required for linking specific sources to contamination. However, the

study results demonstrate that organic contamination can be associated to the use of sample and tool bags,

glovebox construction materials, laboratory equipment, cleanroom facility construction materials,

cleaning chemicals, and personal hygiene products.

Modern modular cleanroom designs used at JSC since 1999 contain a larger variety of complex organic

construction products (plastics) and adhesive (silicone) components than previous curation facilities.

While these construction products have greatly reduced the particle load and ease of cleaning in the

laboratory environment, they have increased the variety of organic outgassing products. As a result, this

has also increased the difficulty in linking specific outgassing products and hinders efforts to reduce

organic contamination over time. This is not to suggest that previous laboratory construction did not

contain large amounts of organics outgassing, but the possible sources of contamination were easier to

isolate. The application of new construction materials may have increased chemical outgassing over time

when compared with the 1978 constructed Lunar facilities in B31N. In general, most outgassing organic

material will decrease contamination levels over time. This observation is illustrated by the comparison

of Genesis cleanroom organic results between 2000 and 2011. A closer comparison of individual

plasticizers that were found shows that the newer classes of cleanrooms outgassing chemicals are being

detected in the ACG, but not in the LCG. This difference could be related to differences in construction

materials and the amount of time since original installation. A future experiment could clean the ACG

with organic solvents, degreasers, and/or other organic contamination reduction cleaning procedures and

retest for organics. The results could determine the presence or absence of cleanroom related chemicals.

The hydrocarbon contamination is most likely a mix of plastic construction components and the use of

sample and tool bags (mostly nylon and to a lesser extent Teflon). Based on recent organic tests on

nitrogen supply lines in B31 and B31N, the hydrocarbon contamination is not from the supply of nitrogen

and is indigenous to the glovebox. Some of the hydrocarbon and plasticizer contamination found in the

glovebox tests may originate from the polycarbonate windows, gloves (both neoprene and to a lesser

71

extent Hypalon) and possibly a small Viton gasket component. The largest contaminating glovebox

material is most likely the use of polycarbonate windows. This was observed when the MBraun cold

curation glovebox changed from polycarbonate to glass windows for Hayabusa sample containment. The

use of a heat sealer to seal Teflon and nylon bags is probably related to the largest component of silicone

contamination inside the glovebox and cleanroom. The silicon rubber strip could be changed to a more

heat-tolerant product, such as Kalrez, Chemraz, or PEEK, to reduce silicone outgassing contamination. In

addition, heat sealing will also produce outgassing of hydrocarbons. Caprolactam, nylon-6, is still

detectable in large quantities in the lab over Teflon related products. Many solvents found during testing

could be from the daily use of IPA wipes and other cleaning products. In smaller quantities, outgassing

of paint products has been detected in the cleanrooms. The overall organic results show a strong

possibility that personal hygiene products (e.g., soaps, perfumes, nail polish) have been found in JSC

curation laboratories and possibly in lunar gloveboxes diffusing through porous neoprene gloves. Further

testing is required of laboratory material and personal hygiene products to provide a direct correlation

between the specific contaminate and source.

The TSP 23 UPW cleaning for the LCG and ACG showed that the optical stereomicroscope particle

inspection was not as precise as the automated liquid particle counter. In addition, the microscopic

inspection has an element of potential human error. JSC Curation should review new practices for

cleanliness inspection as well as implement better particle counting standards. Historically, JSC Curation

used THC, NVR, black light inspection initiated during the Apollo program. Standard methods for

testing cleanliness at other NASA cleaning facilities still use the NVR approach standard in MIL-STD

1246C and TOC collected from rinse solutions or water. However, X-ray photoelectron spectroscopy

(XPS) could provide a better approach for quickly assessing organic cleanliness. An XPS method for

identifying residual organic contamination on a material surface after precision cleaning was initially

researched by Mickelson (2002a). XPS was also used to assess carbon contamination on Genesis solar

wind samples (Calaway et al. 2007). XPS has the ability to quantify contamination at or below 1015

carbon atoms/cm2, which has better precision than other standard testing and verification of cleanliness

methods. In addition, standards could be manufactured with curation standard material surface with 1014

to 1015

carbon atoms/cm2 and used for daily comparison after precision cleaning.

The study of JSC curation cleaning procedures through time shows that procedural changes are not well

documented. The selection and deletion of chemicals has not been thoroughly studied and focused

cleaning reviews may be required for JSC curation. Specifically, JSC 03243 and TSP 23 glovebox

cleaning procedures are in need of further review. It may also be useful to closely study the history of

changes over time and chemical substitutions (e.g., JSC 03243 Oct. 1, 1971, and June 1, 1981, cleaning

procedures). The two major chemical changes for cleaning were the use of IPA over 3:1

Benzene/Methanol solution and the use of UPW over Freon 113. Freon 113 had the additional benefit of

being a useful organic degreasing solvent as well as a good chemical for final rinsing. The addition of

Freon 113 to Apollo 11 cleaning procedures significantly helped to reduce organic contamination. A

substitute for Freon has not been thoroughly studied and this was also mentioned by several historical

reports. New chemicals have replaced Freon for cleaning in other industries (e.g., Dupont Vertrel XF

(HFC-4310), 1,1,1,2,2,3,4,5,5,5 – decafluoropentane and 3M HFE-7100DL, a methyl nonafluoroisobutyl

ether). The TSP 23 UPW cleaning procedure was recently established to only use UPW and UPW is the

choice for final rinsing in the semiconductor industry. However, the semiconductor industry also uses

many different cleaning agents before a final UPW rinse to reduce organic contamination. In addition,

accepted practices for the semiconductor industry may not directly translate to a cleanliness policy for

such a diverse collection of extraterrestrial samples. Nevertheless, UPW has a very high purity, free from

72

inorganic and organic contamination and is much cleaner than most manufactured solvents that require

complex distillation purification systems. If UPW is continued to be used at JSC curation, the system

should be maintained and have an established monitoring program based on international standards.

Established monitoring practices of the UPW systems includes: ASTM D 5127-13, a standard guide for

the use of UPW; ASTM D4453 – 11, a standard for handling UPW; ASTM D 5391-99 test method for

flowing UPW resistivity; ASTM D 5997-96 test methods for monitoring UPW total organic carbon; and

ASTM F 1094-87 test methods for microbiological monitoring of UPW.

Another observation from TSP 23 UPW cleaning was the state of the cleanroom used for cleaning. The

Apollo program used ISO class 5 cleanrooms for all cleaning. Today, JSC curation Final Clean

laboratory uses a clean tent at about ISO Class 6 to 7. Since many new curation laboratories use ISO

Class 4 and 5 cleanrooms, it may be a good practice to match the cleaning facility at the same cleanliness

level as the cleanest cleanroom (ISO class 4 in this case). In most modular cleanroom facilities in the

semiconductor industry, it is common practice to design the cleanroom for in-situ cleaning and clean

everything in-place. A review of the JSC cleaning facility could study the type of cleanroom needed for

cleaning curation isolation containment and handling equipment in-place as opposed to outside of the

laboratory. In addition, it would be important to look at how the individual laboratories are physically

connected to the cleaning process and if detached, how this affects clean products in transit to the lab.

The construction of new laboratories should be designed with cleaning in mind of how it will be

physically done and provide adequate space to clean equipment and lab. Technicians were also observed

wearing lab coat, shoe cover, and hat in the Final Clean lab and inside the Lunar lab during TSP 23.

However, most modern precision cleaning is done with full cleanroom suit with hood, masks, and double

gloves – especially if you are opening the isolation containment system (glovebox). Any future cleaning

facility study should also investigate the prevention of contamination by laboratory cleaning technicians

and the appropriate use of cleanroom garments and personnel hygiene requirements. The last in-depth

literature reviews on curation cleaning practices were done in 2002 as part of the NASA report series on

Mars Return Sample Handling (MRSH). Edward Mickelson (2002a, 2002b, 2002c) provided three

reports on cleanliness standards, methods for monitoring cleanliness and best practices for cleaning in a

curation laboratory. However, these reports are becoming outdated and a new focused literature study on

current state-of-the-art cleanliness standards, method of cleaning, types of materials to use, and

monitoring cleanliness would be beneficial to JSC curation.

The organic contamination baseline study also demonstrated the necessity of a focused material review.

Sample segregation and material selection are both important for reducing organic contamination. The

segregation of samples was highlighted in the Bada Committee final report. Specifically, the isolation

and containment of samples from lab personnel and certain materials are important. In addition, the

purchasing of approved materials must be carefully monitored. For example, Viton, a DuPont registered

trademark fluoroelastomer, is routinely used as a gasket material for gloveboxes in JSC curation.

However, DuPont currently sells 37 types of Viton with each having different outgassing and particle

shedding properties. While curation may require a Viton material, specific Viton needs to be specified.

This becomes more complicated when a secondary company is supplying the Viton part needed for

primary curation of samples and this material called “Viton” may not necessarily be manufactured by

DuPont. Materials that are purchased by JSC curation should be certified by the manufactures or vendor

to reduce the chance that the received product is not counterfeit. Sample segregation for inorganic and

organic analysis may need separate isolation containment systems constructed from different material.

For example an organic processing glovebox materials list may include:

73

Stainless Steel 316L (main chamber)

DuPont Kalrez seals

Schott Amiran Anti-reflective Glass

Honeywell North polyurethane/chlorosulfonated polyethylene gloves

In-line Hydrocarbon gaseous nitrogen purifier

In-line Pall 3nm particle gaseous nitrogen filter

Stainless Steel 316L containers

Inorganic processing glovebox materials list may include:

Ethylene chlorotrifluoroethylene, Halar from Edlon Inc. SC-2001 non-pigmented (main

chamber)

DuPont Kalrez seals

Sabic MR10 Lexan (polycarbonate)

Honeywell North polyurethane/chlorosulfonated polyethylene gloves

In-line Pall 3nm particle filter

Teflon containers

Throughout the 40 years of JSC curation, the use of Teflon, nylon and polyethylene bags in labs as well

as heat sealing these types of bags for primary sample containment has been a topic for discussion and

study. Historically, the Apollo program used only Teflon as the primary sample containment and for

handling samples with over-gloves in a glovebox. Nylon and polyethylene are certainly detectable and

large contamination sources in curation labs. While the cost of nylon and polyethylene is much lower

when compared to the expense of Teflon, more studies are needed to fully understand the short-term and

long-term use of these materials as primary containment. In addition, a review of permissible glovebox

glove materials and routine replacement is recommended. The LCG organic testing and historical records

demonstrated that there might be contamination from personnel hygiene products diffusing through

neoprene glovebox gloves in lunar gloveboxes. Neoprene may need to be changed to Hypalon or another

comparable material. The lunar gloveboxes use of polycarbonate over glass should also be reviewed.

The initial switch to polycarbonate (Lexan) in the Lunar laboratory was never documented or studied. In

addition, polycarbonate windows in Lunar lab gloveboxes were observed to be visibly deteriorated

(discolored breakdown of the plastic as well as numerous scratches). Routine replacement should be

explored for polycarbonate materials (possible every 10 years, which is the recommendation for most

Lexan manufactures). While glass windows will reduce organic contamination, glass is prone to break

during geologic subdivision with hammering; although the Apollo 15 Lunar processing cabinet still has

the original glass window. Safety issues may require polycarbonate or a more complex multiple layered

window to accommodate safety and cleanliness may need to be designed and manufactured. All material

used in curation must be thoroughly tested before use (e.g., the Viton example above). JSC curation

should also keep a good record of material testing or the manufacturer’s material tests. In addition,

modular cleanroom construction materials and facility maintenance (e.g., new floors, walls, GN2 piping,

etc.) materials need to be studied thoroughly before installation.

Facility maintenance and routine cleaning documentation was observed to be absent in the JSC curation

data center and difficult to trace. While the Apollo program once used contractor TSP reports and kept

adequate records, this is currently not done today. Each glovebox, cabinet, and sample handling tools

74

should have a documented cleaning history, easily assessable and known. In addition, each glovebox,

cabinet, and sample handling tools should have a minimum standard for cleaning and be placed on a

schedule for recleaning at an established shelf-life (possibly annual). Tools and samples that are bagged

are prone for bag material degradation over time and each bag should be on a cleaning and re-bagging

schedule. Laboratory furniture, instrumentation, floor, and wall cleaning should be regular and have a

documented cleaning history. While procedures and schedules exist for cleaning certain curation labs,

thorough documentation does not exist of what was cleaned or when. For gloveboxes, each material

component should have a life-span and replacement schedule. For example, Viton gaskets and

polycarbonate (Lexan) windows manufacturers typically recommend replacement every 10 years, and

glove manufacturers typically recommend replacement every 5 years. The GN2 piping infrastructure

must be routinely inspected for possible sources of cross-contamination between laboratories and

isolation contaminant systems. New GN2 piping also must be carefully documented such that each pipe

and valve is certified cleaned. Any new augmentation to the system must have proper materials and be

cleaned in-house or certified cleaned from the manufacturer. GN2 filters and purifiers should also be

placed on a replacement schedule. Most manufacturers typically recommend annual replacement or when

a specified gas volume has passed through the filter. As filtration systems improve, GN2 filter upgrades

are recommended (e.g., Lunar lab has old 60 µm filtration and today filtration can be readily available at

0.3 nm filtration). For reducing organics in the GN2 system, in-line point-source hydrocarbon traps could

be added to the GN2 system at specific gloveboxes or storage systems. As part of a regular facility

maintenance schedule, routine inorganic and organic monitoring of all curation laboratories would benefit

from early detection of contamination and potentially help understand point sources of contamination.

The JSC curation story of Xylan contamination raised several potential lessons learned that should be

studied for progressing modern curation practices and mission planning. The rapid schedule and lack of

resources for material testing in the early 1970s started the use of Xylan in the labs without being

thoroughly investigated. The initial testing was never completed as required by the contamination control

committee. In addition, the committee changed personnel and the committee itself was eventually

dissolved without closing tasks and actions. A long period of time is observed between when Xylan

contamination was officially noticed by the contamination control officer to actual laboratory actions

(1986 to 1990). A breakdown in communication due to interoffice politics and management prolonged

actions to investigative scientific study. The Xylan study also recognized that polyamides in the

gloveboxes could potentially give a false biochemical signal. It was suggested that polyamides in the

Xylan could possibly affect research analyses of amino acids and proteins. However, only JSC curation

internal memos documented this hypothesis and this interpretation of the data set was not noted in the

final Xylan reports. This would later be noted in the study of nylon bags, almost a decade later. If Xylan

was researched thoroughly in the 1970s and early 1980s, the increased use of nylon and caprolactam

organic contamination may have been avoided.

Administrative procedures and employee training can help reduce organic contamination in JSC curation

laboratories. Annual training on cleaning and working in cleanrooms could be used to help employees

remember protocols and introduce new standards. Many NASA wide cleanroom certification training

classes are a one-time occurrence and do not meet cleanroom training requirements needed for

cleanrooms rated below ISO class 7. At JSC, the curation facilities house the cleanest facilities at JSC.

The training should be tailored to curation cleanroom requirements and not rely on NASA-wide training.

It is suggested that a NASA training policy for all workers in curation laboratory be well established and

each employee should learn how to be vigilant toward contamination sources. During the historical

literature search, it was found that official memoranda were widely used prior to 1995. This type of

75

interoffice reporting was critical for understanding historical curation decisions or changes in procedures.

However, with the advent of email, there is no system or memos to document historical changes to

curation facilities or procedures. A new archiving system is required to track this information for future

generations to understand past laboratory and procedural changes.

In the past, JSC Curation used a full-time CCO who monitored the laboratories and routinely would

report to CAPTEM. Today, the CCO is a full-time researcher with a low percentage of time dedicated to

curation contamination oversight. The idea of the CCO as a full-time job to focus on monitoring

contamination in all curation laboratories should be carefully reviewed. The CCO could also be used to

maintain a robust research program on material testing, cleaning technologies, and infrastructure

improvements. CAPTEM should also review the idea of a contamination subcommittee with a dedicated

chair, which could also be the CCO. The new contamination control subcommittee would be comprised

of a member from each collection subcommittee. Scheduled lab inspections and documentation for

contamination, similar to the safety inspections, could be conducted routinely by lab leads (weekly), CCO

(monthly) and CAPTEM (annually). Each curation collection could be mandated to keep documentation

on cleaning history and monitoring data for review by the CCO.

The Apollo program was the last sample return mission that made specific requirements for organic

contamination. The Lunar mission required an organic cleanliness level of < 1 ng/g, which was the

detection limit of the time. However, today NASA does not maintain organic cleanliness policies or

requirements for future sample return mission beyond the basic requirements from the Planetary

Protection Office. Future mission planning would benefit from basic requirements for organic

contamination and cleanliness levels from a scientific perspective. These requirements could be

established by the planetary science subcommittee and CAPTEM under the NASA Advisory Council.

The requirements could then be administered as NASA Policy Directives through the Astromaterials

Acquisition and Curation Office at JSC. If today’s scientific community requires an organic free

environment for future sample return missions that are better than the observed organic loads in JSC

Curation, more can be done on choosing better materials as well as modifying current handling and

cleaning procedures.

The organic contamination baseline study has produced the most comprehensive study on organic

contamination in NASA JSC Astromaterials Acquisition and Curation Office laboratories. The historical

perspective and testing results can be used as a benchmark to plan new sample return mission

requirements that wish to preserve extraterrestrial organic material from sample collection to the curation

facility. The results of this study highlight current procedures and requirements that will require

improvement to match the cleanliness of the Apollo program and even further innovations to meet the

requirements for future sample return missions. The study also provides more avenues of research on

contamination monitoring and control in a curation facility. While this report is a comprehensive review

of organic contamination that has been done to date at JSC, the recent contamination monitoring has

mainly focused on organic contamination > C7 hydrocarbons and compounds. Future research and

monitoring will need to extend the organic baseline study to include light organics C1 to C6 that will be

increasingly important for future missions. In addition, the nature of terrestrial organic contamination

from PAHs, bacteria (DNA and RNA), amino acids, and other biological studies will be paramount for

future exploration missions that focus on astrobiology. This new line of research will take several more

years of study and progress JSC curation’s ability to further understand the role of organics and mitigate

contamination.

76

5.0 APPENDIX I

Identified Organic Compounds in Johnson Space Center Curation Laboratories

This is a list of all identified organics compounds found in JSC Curation B31 and B31N from 1998 to

2013:

1-(2-Butoxyethoxy) ethanol

2-(2-Butoxyethoxy) ethanol

2-(2-Butoxyethoxy) ethanol + Cyclo (Me2SiO)7

2-(2-Butoxyethoxy) ethanol + Cyclo(Me2SiO)5

2, 6-di(t-butyl)-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one

2, 6-di-butyl-2,5-cyclohexadiene-1,4-dione

2, 6-di-tert

2, 6-di-tert-Butylquinone

2-Butoxypropanol

2-Ethylhexanol

2-Nitropropane

2-n-Octyl-3 (2H)-lsothiazolone

2-Octyl-3-isothiazolinone

2-Propanol, 1-(2-methoxypropoxy)-

3, 5-di-tert-Butyl-4-hydroxybenzaldehyde

4-(hydroxymethlethyl)-acetophenone

Acetaldehyde

Acetone

Acetonitrile

Acetophenone

Acetophenone derivative

Acetyl acetophenone

Acetyl phenyl propanol

Acrolein

Adipic acid derivative

Alkyl acrylate

Alkyl ester + Cyclo(Me2SiO)6

Alkyl esters

Alkyl nitrile

Alkyl phthalate

Alkylphenol

Benzene

Benzaldehyde

Benzoic acid + 2-(2-butoxy ethoxy) ethanol

Benzoic acid + Decanal

BHT-aldehyde

BHT-quinone-methide + Ethanone, 1-[4-(1-hydroxy-1-methylethyl) phenyl]-

Butanol

Butanol + benzene

Butene

Butoxy ethanol

Butoxyethoxy ethanol

Butoxypropanol

Butyl benzyl phthalate

77

Butyl hydroxy toluene (BHT)

Butylbenzoquinone

Butyraldehyde

C3 – benzene + dipropylene glycol

C7 Ketone

C7 Saturated aliphatic hydrocarbons

C6 Hydrocarbons

C8 Hydrocarbons

C9 Aromatic Hydrocarbon

C12 Hydrocarbon + Unknown(m/z:97,110)

C14 Saturated aliphatic hydrocarbons

C20 Hydrocarbon

C5 – C9 Hydrocarbons

C6 – C10 Hydrocarbons

C6 – C7 Hydrocarbons

C6 – C9 Hydrocarbons

C8 – C23 Hydrocarbons

C8 – C25 Hydrocarbons

C8 – C9 Saturated aliphatic hydrocarbons

C8 – C9 Saturated and unsaturated aliphatic hydrocarbons

C10 – C11 Saturated aliphatic hydrocarbons

C10 – C12 Saturated aliphatic hydrocarbons

C10 – C13 Saturated aliphatic hydrocarbons

C10 – C25 Hydrocarbons

C11 – C18 Hydrocarbons

C16 – C20 Hydrocarbon

C18 – C27 Hydrocarbons

C20 – C24 Hydrocarbons

C21 – C25 Hydrocarbons

C21 – C26 Hydrocarbons

Caprolactam

Carbon disulfide

Carbon monoxide

Carbonyl sulfide

Cyclic tetramehtylene adipate

Cyclo (Me2SiO)3

Cyclo (Me2SiO)4

Cyclo (Me2SiO)5

Cyclo (Me2SiO)6

Cyclo (Me2SiO)7

Cyclo (Me2SiO)7 + 2,6-di-tert-butyl benzoquinone

Cyclo (Me2SiO)8

Cyclo (Me2SiO)9

Cyclo (Me2SiO)10

Cyclo (Me2SiO)11

Cyclododecane

Cyclooctasiloxane, hexadecamethyl-

Decamethylcyclopentasiloxane

Di(2-ethylhexyl)adipate

Diacetoxy butane

Diacetyl acetophenone

Diacetyl benzene

78

Dibutyl phthalate (DBP)

Dibutylamine

Didecyl ester of decanedioic acid

Didecyl sebacate

Diethyl phthalate (DEP)

Difluorodimethyl silane

Diisobutyl phthalate

Diisopropenyl benzene

Diisopropyl adipate

Diisopropyl phenol

Dimethyl benzyl amine

Dimethyl phthalate

Dimethylcyclohexanol

Di-n-octyl phthalate

Dioctyl adipate

Dioctyl phthalate (DOP)

Dipropylene glycol methyl ether

Dipropyleneglycol

Dodecanamide

Dodecanenitrile

Ethanol, 2-(2-butoxyethoxy)- + Cyclo(Me2SiO)5

Ethyl benzene

Ethyl hexanol

Fluorocarbons

Hexadecamethylheptasiloxane

Hexamethylcyclotrisiloxane

Hexamethyldisiloxane

Hexanedioic acid, bis(2-ethylhexyl) ester

Hydroxymethylethyl-acetophenone

Isobutyraldehyde

Isopropanol

Isopropenyl acetophenone

Isopropenyl acetophenone + Cyclo (Me2SiO)6

Isopropenylbenzene

Isopropyl alcohol

Isopropyl myristate

m, p-Xylenes

Methoxypropoxypropanol

Methyl isobutyl ketone (MIBK)

Methyl isopropyl ether

Methyl naphthalene isomers

Methyl palmitate

Methylethylketone

N, N-dimethyl formamide

Naphthalene

Naphthalene + Butoxethoxy ethanol + Cyclo (Me2SiO)5

NMP

N-N-dibutylacetamide

Nonanal

Octamethylcyclotetrasiloxane

Octasulfur

Other siloxanes

79

o-Xylene

p-Acetyl acetophenone

p-Acetyl-isopropenylbenzene

p-Diacetylbenzene

PGMEA

Phenols

Possible fluorochlorocarbons (m/z: 85, 101, 135,151)

Propoxypropanol

Propylene glycol glyme isomers

Siloxane

Styrene

Sulfur dioxide

Surfynol

Tetrachloroethylene

Texanol

Toluene

Trichloroethylene

Triethyl phosphate

Triphenyl phosphate

Tripropylene glycol

TXIB

TXIB + Diethyl phthalate

Undecanenitrile

Unknown (43, 71, 115, 145, 160)

Unknown (m/z: 111, 125, 140)

Unknown (m/z: 115, 145, 160)

Unknown (m/z: 115, 158)

Unknown (m/z: 138, 208)

Unknown (m/z: 153, 183, 198)

Unknown (m/z: 41, 55, 84,100, 129)

Unknown (m/z: 43, 161, 176)

Unknown (m/z: 43, 163)

Unknown (m/z: 43, 55, 115, 127)

Unknown (m/z: 43, 55, 127, 155, 183)

Unknown (m/z: 43, 55, 71, 95)

Unknown (m/z: 43, 56, 71, 173)

Unknown (m/z: 43, 57, 101, 127)

Unknown (m/z: 55, 84, 112, 142)

Unknown (m/z: 55, 84, 99, 173)

Unknown (m/z: 55, 97, 150)

Unknown (m/z: 55, 99, 173)

Unknown (m/z: 55, 99, 173, 221 )

Unknown (m/z: 57, 165, 267, 282)

Unknown (m/z: 70, 77, 105,112, 123)

Unknown (m/z: 71 , 83, 101 , 113, 119)

Unknown (m/z: 76,104,149,193)

Unknown (m/z:43, 55, 71, 97, 110)

Unknown (m/z:43,57,71,83,101,113,119,132, 147)

Unknown (m/z:43,71,91,115,145,160) + Cyclo(Me2Sio)6

Unknown (me/: 43, 163)

Xylenes

80

6.0 APPENDIX II

Johnson Space Center 03243 Glovebox Cleaning Procedure: 1981

Lunar Sample Curatorial Facility Cleaning Procedures for Contamination Control: JSC 03243, June 1,

1981 (supersedes JSC 03243). Except from CP-1 pages 4-7:

CP-l

1.0 PROCEDURE FOR CLEANING LUNAR SAMPLE CABINETRY

1.1 PROCEDURE

A. This procedure shall be followed to clean stainless steel GN2 cabinetry for processing and

storage of lunar samples. This procedure may also be followed to clean cabinetry for other

events requiring this level of cleanliness

B. Degreasing - Degreasing is required on all interior surfaces of new cabinets during first

cleaning. Degreasing on previously cleaned cabinets is required only when visual

inspection indicates need, or when called for on work request.

C. New cabinets, not previously cleaned, will be given an initial acid wash to remove lead

contamination derived from the fabrication process. After the first cleaning, acid wash will

not be required unless operations dictate otherwise. Acid wash will be specified on the

Clean Room Work Request (SOG) when required.

1.1.1 PREPARATION

A. Personnel involved in cleaning will wear clean-room clothing when working in cabinetry.

B. Make up 1% Liquidet solution using facility distilled water, meeting particle count

requirements of table IV. Certify daily.

C. Acid Wash (when required) - Make up 2% nitric acid solution using reagent grade acid and

facility distilled water.

1.1. 2 Cabinet Cleaning

A. Degrease according to Para. 1.1.3 when called for on Work Request.

B. Completely wash all areas inside of each cabinet with Liquidet solution. Use stiff nylon

brush, and nonabrasive scouring pads to scrub and polish the cabinet surfaces. Remove all

visible rust and stains with Scotch Brite pads or stainless steel toothbrush.

C. Remove all solution from cabinet. Use vacuum flask with liquid pickup, lint-free wipes,

and squeegee as needed.

D. Rinse all areas with distilled or deionized water. Use drain or vacuum to remove the

solution.

81

E. Repeat water rinses and removal until all of the detergent is gone. Rinse with isopropyl

alcohol and purge with GN2 until dry.

Examine all interior surfaces with a black light inside the cabinet. If there is no

fluorescence, proceed to the next step. If there is fluorescence:

1. Reclean the fluorescent areas.

2. Reexamine with black light. If there has been no change in the fluorescence,

proceed to the next step. If there is a change in the fluorescence, repeat cleaning and

rinsing until there is no further reduction.

NOTE

NEVER LEAVE WATER IN CABINET FOR EXTENDED PERIODS OF

TIME, AS THIS WILL PROMOTE RUST. IF ANY SEQUENCE IS

INTERRUPTED AND A DELAY OCCURS, REMOVE WATER FROM

CABINET WITH ISOPRDPYL ALCOHOL RINSE AND PUT CABINET

UNDER GN2 PURGE.

F. Using an unfiltered Millipore can at 85 psig, spray interior of cabinet with 1% Liquidet

and water solution.

G. Repeat water rinses and removal until all of the detergent is gone.

NOTE

PLACE TEFLON OR POLY GLOVE PORT COVERS IN POSITION.

COVERS MAY BE REMOVED TO PROVIDE ACCESS FOR

CLEANING, BUT SHOULD BE REPLACED WHEN ACCESS IS NOT

REQUIRED. PERSONNEL WILL WEAR TEFLON FEP GLOVES ON

ALL SUBSEQUENT STEPS REQUIRING OPERATIONS INSIDE THE

CABINETS.

H. Immediately after water rinse, rinse all areas with isopropyl alcohol (IPA) (85 psig

pressure) to remove water.

I. Remove all solution from cabinet. Use vacuum flask with liquid pickup and squeegee as

needed. Dry cabinet with GN2 purge.

J. Acid wash per Para. 1.1.4 only when specified on Work Request .

K. Rinse all areas with a minimum of 500 ml redistilled Freon per square foot of cabinet

surface. Freon shall be at 85 psig pressure.

L. Remove all Freon from cabinet. Use vacuum flask with liquid pickup and squeegee if

needed.

82

M. Use a 5 gallon stainless steel pressurized (85 psig) spray can of redistilled Freon for

final verification of cabinet cleanliness. Before flushing, take 1000 ml Freon base

sample. Flush .the interior of the cabinet with a minimum of 100 ml per square foot of

surface area. Collect a minimum of 700 ml representative sample and another 1000 ml

sample at end of flushing cycle.

N. Perform a particle count on the 1000 ml sample. Deliver the base sample and 700 ml

sample to lab for total hydrocarbon count (THC & NVR) analysis. The particle count

and THC or NVR of final flush shall meet table IV requirements.* The base sample

shall meet table I* requirements for THC or NVR. Any failure to meet these

requirements is cause for rejection.

O. Visually inspect interior of cabinet for particulate matter and rust.

1. If particulate matter is found, repeat Steps M and N until cabinet is free of

particulates.

2. If rust is found, use wipes and Freon to remove. Repeat Steps M and N until cabinet is

free of particulates.

P. After verification of cleaning, put a positive purge on the cabinet with gaseous nitrogen

meeting table III* requirements.

*Appendix

1. 1.3 DEGREASING PROCEDURE - Only when called for in work request or when necessary

A. Use high pressure Freon spray on all interior surfaces of cabinet.

B. Scrub floor and walls of cabinet with Teflon brushes or other non-abrasive scrubbers.

C. Repeat high pressure Freon spray on all interior surfaces.

D. Drain Freon and dry cabinet with nitrogen purge to reduce introduction of moisture.

1. 1.4 ACID WASH - Only when called for on work request. Acid wash only floor of the cabinet

A. Prepare adequate 2% nitric acid solution to completely cover floor of cabinet to a depth of

approximately ¼”. Use reagent grade acid: 69 – 71 % HN03 to prepare solution.

B. Plug all drain lines and carefully pour acid solution over floor of cabinet. Let sit 30

minutes. Agitate solution with squeegee after 15 minutes.

C. Drain acid from cabinet.

D. Rinse all areas of cabinet with water.

E. Repeat step "B" and "C".

83

F. Rinse all interior surfaces of cabinet with distilled water until sample caught at drain pipe is

neutral.

G. Rinse all surfaces with pressurized isopropyl alcohol. This will facilitate removal of water.

H. Immediately after alcohol rinse, start GN2 purge of cabinet. Continue purge until cabinet is

dry.

I. Continue with CP – l cleaning.

1.1.5 PRECLEANING OF CABINET EXTERIOR AND STAND

Preclean exterior of cabinet and stand to remove all stains, finger prints, grease and soiled

areas. Remove exterior rust with stainless steel brushes, Scotch Brite, etc. This includes

underside of cabinet and stand.

NOTE

RUST AND DISCOLORATION FROM WELDS ARE CONSIDERED

DIFFERENT AND SEPARATE PROBLEMS. THIS PROCEDURE REFERS

ONLY TO RUST, NOT DISCOLORATION FROM WELDS. CLEAN ROOM

SHOULD COORDINATE WITH CURATORIAL TOOL AND EQUIPMENT

MONITOR ON PROBLEMS.

1.1.6 PREPARATION FOR TRANSFER TO CURATORIAL FACILITY

After final GN2 purge, tighten all fittings and caps on penetrations to prevent introduction

of moisture and loss of nitrogen. After interior and exterior are clean, bag in poly for

transfer to building 31 or 31A/Curatorial Facility.

*APPENDIX

TABLE I – BASE SAMPLE PARTICLE COUNT* THC** NVR***

10µ to 25µ - 15 2µg/100 ml 0.2mg/100ml

25µ to 50µ - 2

50µ to 100µ - 1

> 100µ - zero

*Total number of particles in 100 ml sample. **Total hydrocarbon contamination as determined by gas chromatograph. ***Nonvolatile Residue

84

TABLE II – FINAL FLUSH PARTICLE COUNT* THC** NVR***

0µ to 10µ - unlimited 3µg/ft2*** 1.0mg/ft

2

10µ to 25µ - 100 NVR & THC not applicable to plastics , rubber, other elastomers

25µ to 50µ - 10

50µ to 100µ - 5

100µ to 175µ - 1

> 175µ - zero

*Total number of particles in 100 ml sample. **Total hydrocarbon contamination as determined by gas chromatograph. ***This works out to be 3µg/100 ml based on sampling rate of 100 ml/ft2. ****NVR - Nonvolatile Residue

TABLE III – LIQUID NITRDGEN SPECIFICATION

CONTANINANT MAX ALLOWABLE (PPM)

Argon 20

Oxygen 10

Carbon Monoxide 10

Carbon Dioxide 10

Hydrogen 10

Moisture 10

Methane 1

TABLE IV – PARTICLE COUNT AND THC LIMITS PARTICLE COUNT* THC

0µ to 175µ unlimited** (10µg/ft2 for xylan

coated items) 175µ to 700µ 6

>700µ zero

Fibers;*** NVR

700µ to 1500µ 1 1.0mg/ft2

>1500µ zero

* Total number of particles in 1000 ml sample.

** Unlimited means that particles in this range are not counted; however, any obscuring

of the filter grid lines shall be cause for rejection.

*** Fibers - a particle whose length is 10 times its width (minimum length of 100µ).

*** May be waived by Contamination Control Officer.

85

7.0 APPENDIX III

Technical Support Procedure 23 – Glovebox Cleaning: version March 8, 2011

6. PROCEDURE

Preparations for cleaning the cabinet should be done on the day before the cabinet is scheduled for

cleaning (sections 6.1.1 through 6.1.7) so that cleaning can be started at the beginning of the following

day with washing done continuously, with no breaks, until completion and the cabinet is completely dry.

Allowing water to remain in the cabinet will promote rusting of the stainless steel by the UPW.

6.1 Prepare cabinet for cleaning

6.1.1 Processor will remove all samples and equipment, except the balance and heat sealer, from

cabinet.

NOTE: Remainder of procedure will be done by CTOG.

6.1.2 Lock down balance and remove along with heat sealer.

6.1.3 Dry vacuum the air lock.

6.1.4 Set cabinet flow at 50 SCFH or higher to maintain positive pressure in the cabinet. Remove

gloves and install clean cover sheets one at a time.

6.1.5 If gloves are to be analyzed for biological contamination keep “in cabinet” portion interior and

twisted closed and place in a clean bag.

6.1.6 Tilt the cabinet so that the water will run towards the drain.

6.1.7 Connect the rinse line to the UPW manifold.

6.1.8 Verify that the water is ready

a) Resistivity readings should be > 18 mega ohms (verify by checking the readings taken

that day or check reading on the instrument in 1108)

b) Hot water heater should be “ON”.

6.1.9 Connect the GN2 spray line.

6.1.10 Connect nozzle and wand to rinse line.

6.1.11 Using a Jerri can as a catchment reservoir, connect the drain line to the pump and then on to the

drain. In PSL the drain line will go into drains located on the floor in either 2107 or 2107A.

6.1.12 Spray water into a sink, available container, or drain until the air is out of the line and the line is

rinsed thoroughly.

86

NOTE: When the water is hot determine if protection from the heat is needed. A teflon outer

layer should be used over any item going into the cabinet.

6.1.13 While the water is still flowing, and if specified on the CO, take baseline water samples using

bottle provided. Label containers “Baseline, hot water” with date and time. Appendix A

specifies limits for UPW cabinet rinse.

6.1.14 Sampling UPW for the particles Base Line

a) Rinse the clean vacuum filtration device with certified UPW.

b) Assemble the vacuum filtration device less funnel/filter holder top.

c) Using forceps, remove membrane filter (Millipore, 0.8 microns, preferably black) from

container and place on filter holder base.

d) Attach funnel/filter holder to base.

e) Using a pen, mark area on the pad to indicate area actually filtered.

f) Rinse the funnel/filter holder with water to remove all particles.

g) Turn on vacuum pump and begin pouring sample into the funnel.

h) Allow vacuum pump to run approximately 10 - 20 seconds after all liquid has been

filtered. Turn off vacuum pump.

i) Remove funnel; using forceps place filter pad in clean petri dish.

6.1.15 Counting Procedure for Assaying the Sample.

a) Verify that the microscope is calibrated for the magnification being used.

b) Place petri dish on microscope stage and adjust lamp for maximum particle definition.

Adjust the microscope to the magnification required.

c) Count the pad for particles >10 microns. There must be no more than 50 particles.

Appendix B explains criteria for particle count limits.

d) Initiate a Clean Room Work Request and record particles counted on each step of the

cabinet cleaning. The Clean Room Work Requests are located on Ganymede\Cleaning

Work Request\SOG’s.

6.1.16 If water meets particulate requirement, proceed with cleaning the cabinet.

6.2 Clean the cabinet

6.2.1 Maintain a positive purge on the cabinet at all times. Insert the sprayer and wand

through a slit in the port cover.

87

6.2.2 Clean drain port.

Before rinsing floors and walls, flush hot water through the drain port and discard.

6.2.3 If water samples are to be collected and analyzed, attach approximately 2 ft. of 3/8” clean PFA

tubing to the drain port and cap.

6.2.4 Rinse the cabinet walls with hot water. If hands or arms must extend into the cabinet cover with

clean Teflon over-gloves or bags to prevent the hot water from depositing plastics in the cabinet.

This is especially important if cleaning the Mars meteorite cabinet.

6.2.5 Collect water samples, if specified on the CO. Label collection container “First Rinse” with date

and time.

6.2.6 Continue rinsing using squeegee, Teflon brushes or foam wipes (if allowed) to sweep particles

from floor and into drain.

6.2.7 Empty drain water container if used.

6.2.8 Use the wet vacuum only as necessary in short intervals.

6.2.9 Rinse entire cabinet until walls are warm to enhance drying. Sample the water per 6.1.14 and

6.1.15 until no further significant decrease in particles is attained and there are no more than 50

particles > 10 microns.

6.2.10 If specified on the CO, take “Final Rinse” water samples in the bottles provided and label with

date and time.

6.2.11 Remove the rinse line from the UPW source and connect it to the clean GN2 line. Blow the water

off the top and sides of the cabinet and then towards the drain. (Use the wet vacuum in short

intervals.) Continue blowing water out and towards the drain until it is completely dry.

6.2.12 Install the cover sheets over the glove ports and set a high purge on the cabinet.

6.2.13 Thoroughly dry the PFA tubing with GN2 to prevent microbial growth and cap ends.

6.2.14 If water samples were taken, have analysis done.

Evaluate water analysis results as compared with criteria on Appendix A.

6.2.15 Glove cabinet and prepare for processing.

88

8.0 REFERENCES

Abell, P. I., Cadogan, P. H., Eglinton, G., Maxwell, J. R., & Pillinger, C. T. (1971). Survey of lunar carbon

compounds. I. The presence of indigenous gases and hydrolysable carbon compounds in Apollo 11

and Apollo 12 samples. In Lunar and Planetary Science Conference Proceedings (Vol. 2, p. 1843).

Allton, J. H., Bagby Jr, J. R., & Stabekis, P. D. (1998). Lessons learned during Apollo lunar sample

quarantine and sample curation. Advances in Space Research, 22(3), 373-382.

ASTM Standard D5127 – 13 (2013). Standard Guide for Ultra Pure Water Used in the Electronics and

Semiconductor Industries. ASTM International, West Conshohocken, PA.

ASTM Standard D4453 - 11 (2011). Standard Practice for Handling of High Purity Water Samples. ASTM

International, West Conshohocken, PA.

ASTM Standard D5391 – 99 (2009) Standard Test Method for Electrical Conductivity and Resistivity of a

Flowing High Purity Water Sample. ASTM International, West Conshohocken, PA.

ASTM Standard D5997 – 96 (2009) Standard Test Method for On Line Monitoring of Total Carbon,

Inorganic Carbon in Water by Ultraviolet, Persulfate Oxidation, and Membrane Conductivity

Detection. ASTM International, West Conshohocken, PA.

ASTM Standard F1094 – 87 (2012) Standard Test Methods for Microbiological Monitoring of Water Used

for Processing Electron and Microelectronic Devices by Direct Pressure Tap Sampling Valve and by

the Presterilized Plastic Bag Method. ASTM International, West Conshohocken, PA.

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July 2014 Technical Publication

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Organic Contamination Baseline Study

in NASA Johnson Space Center Astromaterials Curation Laboratories

6. AUTHOR(S) Michael J. Calaway; Carlton C. Allen, Ph.D.; Judith H. Allton

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NUMBERS

Lyndon B. Johnson Space Center

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S-1159

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National Aeronautics and Space Administration

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TP-2014-217393

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13. ABSTRACT (Maximum 200 words)

Future robotic and human spaceflight missions to the Moon, Mars, asteroids, and comets will require curating astromaterial samples

with minimal inorganic and organic contamination to preserve the scientific integrity of each sample. 21st century sample return

missions will focus on strict protocols for reducing organic contamination that have not been seen since the Apollo manned lunar

landing program. To properly curate these materials, the Astromaterials Acquisition and Curation Office under the Astromaterial

Research and Exploration Science Directorate at NASA Johnson Space Center houses and protects all extraterrestrial materials

brought back to Earth that are controlled by the United States government. During fiscal year 2012, we conducted a year-long project

to compile historical documentation and laboratory tests involving organic investigations at these facilities. In addition, we developed

a plan to determine the current state of organic cleanliness in curation laboratories housing astromaterials. This was accomplished by

focusing on current procedures and protocols for cleaning, sample handling, and storage. While the intention of this report is to give a

comprehensive overview of the current state of organic cleanliness in JSC curation laboratories, it also provides a baseline for

determining whether our cleaning procedures and sample handling protocols need to be adapted and/or augmented to meet the new

requirements for future human spaceflight and robotic sample return missions.

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contamination; samples; gloveboxes; clean rooms; Lunar Receiving Laboratory; organic

compounds; sample return missions; space flight 108

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